Positive photosensitive poliymide composition

ABSTRACT

A photosensitive polyimide composition which is soluble in an organic solvent, which is excellent in adhesiveness, heat resistance, mechanical properties and flexibility, which shows the property of highly sensitive positive-type photoresist that is soluble in alkali upon irradiation with light is disclosed. The polyimide composition of the present invention contains a photoacid generator and a solvent-soluble polyimide which shows positive-type photosensitivity in the presence of said photoacid generator.

TECHNICAL FIELD

The present invention relates to a positive photosensitive polyimidecomposition, insulation film formed therefrom and to a method forforming insulation film pattern using the same.

BACKGROUND ART

Photosensitive resin compositions are classified into A)polarity-changing type wherein the polarity of the exposed regions ischanged so that the solubility thereof is changed, B) cutting typewherein chemical bonds are cut by exposure and the exposed regions aresolubilized, and C) cross-linking type wherein cross-linking reactionproceeds so that exposed regions are insolubilized. Thepolarity-changing type may be used as either positive working ornegative working composition depending on the composition of thedeveloping solution. The cutting type may be used as positive workingcomposition, and the cross-linking type may be used as negative workingcomposition in theory. The cross-linking type photosensitive materialshave a disadvantage in carrying out microscopic processing with highresolution that the exposed regions are swollen by the developing withan organic solvent.

In recent years, the molding materials used for overcoating flexibleprinted circuits, interlayer insulation films of multilayer substrates,insulation films and passivation films of solid elements insemiconductor industry, as well as the interlayer insulation materialsof semiconductor integrated circuits and multilayer printed circuitboards are demanded to have good heat resistance. Further, the need toattain higher densification and higher integration demandsphotosensitive heat-resisting materials.

The semiconductor substrates which are used as semiconductor integratedparts in microelectronic industry are covered with photoresists.Photoresist relief structures are formed by forming images andsubsequent development of the photoresist layers. The relief structuresare used as the masks for preparing circuit patterns on thesemiconductor substrates. By this processing cycle, the relief structureof a microchip can be transferred to a substrate.

Photoresists include two different types, that is, positive workingphotoresist and negative working photoresist. These are different inthat the exposed regions of the positive working photoresist is removedby development so that the non-developed regions are left on thesubstrate, while the exposed regions of the negative working photoresistare left as the relief structure. The positive working photoresists haveintrinsically high image resolutions so that they are suited forproduction of VLSIs (large scale integrated circuits).

Conventional positive working photoresists contain a type of novolakresin which is soluble in aqueous alkali and a photosensitive quinonediazide which decreases the solubility of the resin in alkali. When thephotoresist layer is irradiated, the quinone diazide is photoexcited soas to be converted to carboxylic acid, so that the solubility in alkaliof the exposed regions is increased. Thus, by developing the photoresistwith an aqueous alkali, a positive working photoresist relief structureis obtained (U.S. Pat. No. 36,664,735 etc).

The characteristics of the photoresist compositions used in industriesare the solubility of the photoresist in the solvent to be applied, thephotosensitization rate of the photoresist, the developing contrast, thesolubility of the developing solution acceptable from the view point ofenvironment, adhesiveness of the photoresist, dimensional stability athigh temperatures, and abrasion resistance.

The photoresist relief structures obtained by the exposure anddevelopment are usually subjected to heat treatment (postbake) at atemperature of 120° C. to 180° C. The purpose of this treatment is topromote the adhesiveness of the photoresist with the substrate, curingof the photoresist structure, and removal of all of the remainingvolatile components to decrease the erosion in the subsequent etchingstep.

However, in plasma etching, the substrates are subjected to atemperature higher than 200° C. The photoresists containing as the basea novolak resin and a stabilizing improver cannot be thermallystabilized at a temperature of not lower than 180° C.

Polyimide resins are resistant to high temperature of about 400° C. andare stable to chemicals. Therefore, they are useful in formingheat-resisting photoresist layers,

Conventional polyimide photoresists are negative-type photoresists. Thesystem of the negative-type photoresists is based on polyamic acidpolymer having photoreactive side chains. However, this basic materialhas problems in that it has a poor storage stability, a very slowsensitizing rate, and an excess structural shrinkage after developmentand curing (the rate of shrinkage after baking is about 60%). With thiscomposition, to attain a high resolution, exposure of about 10 minutesis necessary. Further, high concentration solutions thereof for formingthick films have especially poor storage stabilities.

With positive-type photoresists, high resolution is attained, exposuretime is short and developing properties with alkali are excellent.Positive working high temperature type photoresist having phenol groupwas developed. A polyoxazole precursor was synthesized by the reactionbetween 3,3′-dihydroxy-4,4′-diaminobiphenyl and isophthalic aciddichloride. This composition is mixed with o-quinone diazide ornaphthoquinone diazide to form a high sensitive positive workingphotosensitive polyoxazole precursor, and polyoxazole having a heatresistance and mechanical properties comparable to those of polyimidemembrane is formed after processing (U.S. Pat. No. 4,339,521 and U.S.Pat. No. 4,395,482).

A solvent-soluble polyimide was synthesized by the reaction ofhexafluoro-2,2-bis(hydroxyaminophenol)propane withhexafluoro-2,2-bis-(dicarboxyphenyl)propane dianhydride (6FDA) or with3,4,3′,4′-benzophenone tetracarboxylic acid dianhydride (BTDA) or with5,5′-oxy-bis-1,3-isobenzofurandione (4,4′-oxydiphthalic aciddianhydride), and positive working photosensitive polyimides wereprepared by mixing the polyimides and o-naphthoquinone diazide,respectively. In this method (Japanese Laid-open Patent Application(Kokai) No. 64-60630 and U.S. Pat. No. 4,927,736), the fluorineatom-containing polyimides are soluble in polar solvents. A novel methodin which polyimide solutions are directly formed by heating thepolyimide at 140 to 160° C. in the presence of p-toluene sulfonic acidas a catalyst was employed. However, to separate the catalyst and thepolyimide, a method in which the polyimide solution is poured intomethanol to recover the polyimide resin as precipitates and theprecipitates are re-dissolved, is employed, which method is unsuitablefor industrial application.

Phenol group or carboxyl group is protected with tetrahydro-2H-pyranylgroup to vanish the solubility in alkali. By adding a photoacidgenerator to the resultant and by irradiating the resulting compositionwith light, an acid is generated. By this acid, the block of thehydroxyl group or carboxyl group is decomposed so that the material isconverted to soluble in alkali. By carrying out heat treatment afterexposure, a plurality of blocks are catalytically removed by the acid,so that an amplification effect is obtained, thereby the composition ishighly sensitized (T. Omote et al.; Macromol., 23, 4788 (1990), K.Naitoh et al.; Polym. Adv. Technol. 4, 294 (1993), K. Naitoh et al.; J.Photopolym. Sci. Technol. 4, 294 (1993), T. Yamaoka et al.;Photosensitive Polyimides Fundamental & Application, 177-211, TechnomicPublish Company Inc. USA(1995)).

A positive-type photosensitive polyamic acid was reported, wherein thecarboxyl group of polyamic acid is converted to ester of 2-nitrobenzylalcohol to prevent dissolution in alkali, and upon irradiation withlight, the ester of the 2-nitrobenzyl group is decomposed to generate acarboxylic acid so that the compound is converted to soluble in alkali(S. Kubota et al.; J. Macromol. Sci. Chem. A24 (10) 1407 (1987), AoYamaoka et al.; Polyfile 2, 14(1990)).

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a photosensitivepolyimide composition which is soluble in organic solvents, which excelsin adhesiveness, heat resistance, mechanical properties and flexibility,which shows properties of alkali-soluble highly sensitive positive-typephotoresist upon irradiation with light.

The present inventors intensively studied to discover that, by combininga solvent-soluble polyimide and a photoacid generator, a highlysensitive positive-type photosensitive polyimide composition which isalkali-soluble upon irradiation with light is obtained, and that theinsulation film made of the positive-type photosensitive polyimidecomposition excels in adhesiveness, heat resistance, mechanicalproperties and flexibility, thereby completing the present invention.

That is, the present invention provides a positive-type photosensitivepolyimide composition comprising photoacid generator and solvent-solublepolyimide which shows positive-type photosensitivity in the presence ofthe photoacid generator. The present invention also provides apositive-type photosensitive resin film prepared by making theabove-mentioned composition, according to the present invention,dissolved in a solvent, into the form of film. The present inventionalso provides a polyimide insulation film having a pattern, which isprepared by coating, on a substrate, the above-mentioned composition,according to the present invention, dissolved in a solvent, drying thecomposition, exposing an image pattern on the composition to irradiationwith light or electron beam, and removing the exposed regions with analkaline developing solution. The present invention further provides amethod for forming a polyimide insulation film pattern comprisingcoating the composition on a substrate, according to the presentinvention, drying the composition, exposing an image pattern on thecomposition to irradiation with light or electron beam, and removing theexposed regions with an alkaline developing solution.

By the present invention, positive-type photosensitive polyimidecompositions which are alkali-soluble upon irradiation with light wereprovided. The positive-type photosensitive polyimide compositionsaccording to the present invention have high sensitivities. That is,with the polyimide compositions according to the present invention, veryhigh imaging resolutions are attained. The insulation films made fromthe positive-type photosensitive polyimide compositions according to thepresent invention are excellent in adhesiveness, heat resistance,mechanical properties and flexibility. Therefore, the insulation filmsare of polyimide having high heat resistance, electric insulation andadhesiveness, so that they may be widely used in the field of productionof semiconductors, electronic parts and the like.

BEST MODE FOR CARRYING OUT THE INVENTION

As mentioned above, the positive-type photosensitive polyimidecomposition according to the present invention comprises a photoacidgenerator and a solvent-soluble polyimide which shows positive-typephotosensitivity in the presence of the photoacid generator.

The term “photoacid generator” herein means a compound which generatesan acid upon irradiation with light or electronic beam. Since thepolyimide is decomposed by the action of the acid and is soluble inalkalis, the photoacid generator employed in the present invention isnot restricted and any compound which generates an acid upon irradiationwith light or electron beam may be employed. Preferred examples of thephotoacid generator include photosensitive quinone diazide compounds andonium salts.

Preferred examples of the photosensitive quinone diazide compoundsinclude esters of 1,2-naphthoquinone-2-diazide-5-sulfonic acid and1,2-naphthoquinone-2-diazide-4-sulfonic acid, the counterparts of theesters being low molecular aromatic hydroxyl compounds such as2,3,4-trihydroxybenzophenone, 1,3,5-trihydroxybenzene, 2-methylphenol,4-methylphenol and 4,4′-hydroxy-propane. Preferred examples of the oniumsalts include aryl diazonium salts such as 4(N-phenyl)aminophenyldiazonium salt; diaryl halonium salts such as diphenyl iodonium salt;triphenyl sulfonium salts such asbis{4-(diphenylsulfonio)phenyl}sulfide, and bis-hexafluoroantimonate,but the preferred onium salts are not restricted to these.

The polyimide contained in the polyimide composition according to thepresent invention consists essentially of one or more aromatic diaminecomponents and one or more aromatic acid components, and is produced bydirect imidation reaction between one or more aromatic diamines and oneor more aromatic tetracarboxylic dianhydrides.

Preferred examples of the aromatic diamine components (described in theform of monomers) constituting the polyimide contained in the polyimidecomposition according to the present invention include4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether,bis(4-phenoxy)1,4-benzene, bis(4-phenoxy)1,3-benzene,bis(3-phenoxy)1,3-benzene, 2,2-bis(4-aminophenyl)propane,1,1,1,3,3,3-hexafluoro-2-bis(4-aminophenyl)propane,4,4′-diaminophenylmethane, bis(4-aminophenoxy)4,4′-diphenyl,2,2-bis{(4-aminophenoxy)phenyl}propane,2,2-bis{(4-aminophenoxy)phenyl}hexafluoropropane, 1,3-diaminobenzene,1,4-diaminobenzene, 2,4-diaminotoluene,3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)benzidine,α,α′-bis(4-aminophenyl)-1,4-diisopropylbenzene,bis(4-aminophenoxy)-1,3-(2,2-dimethyl)propane and diaminosiloxane. Thesearomatic diamine components may be employed individually or incombination.

Preferred examples of the aromatic acid components (described in theform of monomers) constituting the polyimide contained in the polyimidecomposition according to the present invention include3,4,3′,4′-benzophenone tetracarboxylic dianhydride,3,4,3′,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride,3,4,3′,4′-biphenyl ether tetracarboxylic dianhydride,1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,3′,4′-biphenylsulfone tetracarboxylicdianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylicdianhydride, 4,4′-{2 and2,2-trifluoro-1-(trifluoromethyl)ethylidene}bis(1,2-benzene dicarboxylicdianhydride). These aromatic acid components may be employedindividually or in combination.

It is preferred to employ one or more aromatic diamines, which have oneor more carbonyl groups, nitro groups, methoxy groups, sulfonic groups,sulfide groups, anthracene groups or fluorene groups (hereinafterreferred to as “photosensitive aromatic diamine”), as the one or morearomatic diamines constituting the polyimide, because they are easilyphotoexcited upon irradiation with UV after adding a photoacidgenerator, so that images can be formed with high sensitivity and highresolution with smaller dose of irradiation.

As the preferred photosensitive aromatic diamines, firstly,dialkyl-diamino-bisphenyl sulfone and dialkoxy-diamino-biphenyl sulfonesuch as 3,3′-dimethyl-4,4′-diamino-biphenylsulfone and3,3′-dimethoxy-4,4′-diamino-biphenylsulfone are exemplified. Thepolyimides containing such biphenyl sulfones are linear polymers havinghigh mechanical strengths and high moduli of elasticity, so that theyare studied as highly elastic polyimide fibers, and also as gasseparation membranes because they can be made into films. They can beused as fibers or films, and also as photosensitive films. As shown inthe Examples below, these polyimides containing biphenyl sulfone do notshow photosensitivity even if Michler's ketone which is a sensitizer ora radical generator is added. It was discovered, however, that they aresoluble in alkalis by irradiation with light after adding a quinonediazide compound. Even if the molecular weight (based on polystyrene) ischanged to 30,000, 50,000 and 100,000, the polyimides are soluble inalkalis. From this fact, it is thought that the quinone diazide isphotodecomposed to generate a radical and simultaneously to be convertedto indene acid, and the product interacts with the polyimide groups andbiphenyl sulfone groups, so that the polyimide is converted to bealkali-soluble. That is, by UV irradiation, the quinone diazide compoundis photodecomposed and indene acid is further generated. As a result,the alkyl group or alkoxy group on the biphenyl group is activated sothat the sulfone bond is cleaved, and indene acid is added thereto,thereby increasing the solubility of the polyimide in alkalis.

Additional preferred examples of the photosensitive aromatic diaminesinclude 9,9-bis(aminophenyl)fluorene and9,9-bis(aminoalkyl-phenyl)fluorene. The polyimides containing suchfluorenes are linear polymers having high mechanical strengths and highmoduli of elasticity, so that they are polyimides having excellent filmproperties, and having excellent properties when formed into gasseparation membranes. They can be used as fibers or films, and also asphotosensitive films. As shown in Examples below, these polyimides donot show photosensitivity even if Michler's ketone which is a sensitizeror a radical generator is added. It was discovered, however, they areconverted to be soluble in alkalis by irradiation with light afteradding a quinone diazide compound. Even if the molecular weight (basedon polystyrene) is changed to 30,000, 50,000 and 100,000, they interactwith the radical and the acid produced by photolysis of the quinonediazide to form alkali-soluble polyimides, which give clearpositive-type images. More particularly, 9,9-bis(aminophenyl)fluorene issynthesized from fluorenone and aniline in the presence of an acidcatalyst (Beilstein 13,III,548a). Fluorenone is a photosensitizer whichis used as widely as Michler's ketone and benzanthrone. Althoughfluorenone-containing polyimides are sensitized by irradiation withlight, they are usually not photodecomposed. It was discovered, however,if a quinone diazide co-exists, the quinone diazide generates a radicalby irradiation with light, and radical becomes indene acid thatinteracts with the polyimide, so that thebis(aminophenyl)fluorene-containing polyimides are soluble in alkalis.This is presumably because that the SP3 carbon structure at the9-position of the bis(aminophenyl)fluorene group in the polyimide chainis temporarily stabilized by resonance and is changed to SP2 carbonstructure, so that the aniline group is eliminated and the polyimidechain is cleaved. Various fluorenone derivatives are known. For example,there are 2-nitro compounds, 2,7-dinitro compounds and 7-chlorocompounds. Similarly, as for aniline, various derivatives such as2-methylaniline and 2-methoxyaniline are known. From the above-describedfluorenone derivatives and the aniline derivatives, various9,9-bis(aminophenyl)fluorene derivatives are produced in the presence ofan acid catalyst. These derivatives also constitute positive-typephotosensitive compositions. By using benzathrone compounds in place ofthe fluorenone, positive-type photosensitive polyimide compositions arealso obtained.

Additional preferred examples of the photosensitive aromatic diaminesare nitro aromatic diamines. In 1,4-diamino-2-nitrobenzene and/or3,3′-dinitro-4,4′-diaminobiphenyl, the O atom of nitro radical interactswith the N atom of imide bond. Nitro group and benzene ring are excitedby electron resonance upon irradiation with light, and the oxygen atomin the nitro group acts on the N atom in the imide group to increase theelectron effect. It is presumed that the proton generated from thediazoquinone by light irradiation attacks the N atom in the imide bondto cut the imide bond to generate amide bond, and thus the polyimide issoluble in alkalis. Preferred examples of the nitro aromatic diaminesinclude 1,4-diamino-2-nitrobenzene, 1,5-diamino-2-nitrobenzene,3-nitro-4,4′-diaminobiphenyl, 3,3′-dinitro-4,4′-diaminobiphenyl and thelike. Among these, 1,4-diaminonitrobenzene and3,3-dinitro-4,4′-diaminobiphenyl are especially preferred.

Another preferred example of the photosensitive aromatic diamines is1,5-diaminoanthraquinone. In 1,5-diaminoanthraquinone-containingpolyimides, the anthraquinone is easily photoexcited. It is presumedthat the carbonyl radical of imide bond exerts electron effect tocarbonyl radical in anthraquinone, that the proton generated from thediazoquinone by light irradiation attacks the N atom in the imide bondto cut the imide bond to generate amide bond, so that the polyimide issoluble in alkalis. Anthraquinone is also a photosensitizer andpositive-type patterns are effectively formed with small dose of energyirradiation. Compounds which have similar action to that of1,5-diaminoanthraquinone include 2,4-diaminoacetophenone,2,4-diaminobenzophenone, 2-amino-4′-aminobenzophenone,2-amino-5-aminofluorenone and the like, and these compounds may beemployed. Preferably, 1,5-diaminoanthraquinone is used.

Additional preferred examples of the photosensitive aromatic diaminesinclude diphenyl sulfide group-containing diamines such as4,4′-diaminodiphenyl sulfide. In this case, the diphenyl sulfide groupis contained in the main chain. It is presumed that the diphenyl sulfidein the main chain of the polyimide generates an acid upon irradiationwith light in the presence of a quinone diazide and the acid is bound tothe sulfide group so as to convert the sulfide group to thiol, which isalkali-soluble. The diphenyl sulfide groups in the main chain of thepolyimide may be those originated from a diamino compound such as4,4′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide,4,4′-diamino-3,3′-dimethyl sulfide, bis(4-aminophenoxyphenyl) sulfide,thionine or the like. Among these, 4,4′-diaminodiphenyl sulfide which iseasily available and which is highly effective is preferred.

Additional preferred examples of the photosensitive aromatic diaminesare diphenyl disulfide group-containing diamines such as4,4′-diaminodiphenyl disulfide. In this case, the diphenyl disulfide iscontained in the main chain. It is thought that the polyimidescontaining diphenyl disuslfide in the main chain easily bind to theproton generated from the quinone diazide by irradiation with light soas to be converted to two thiol molecules. In fact, disulfide compoundsare more easily cleaved than sulfide compounds and give sharperpatterns. The diphenyl disulfide in the polyimide main chain may beoriginated from a diamino compound such as 4,4′-diaminodiphenyldisulfide, 3,4′-diaminodiphenyl disulfide, 4,4′-diamino-3,3′-dimethyldisulfide, bis(4-aminophenoxyphenyl)disulfide, thionine or the like.Among these, 4,4′-diaminodiphenyl disulfide which is easily availableand which is highly effective is preferred.

Another preferred example of the photosensitive aromatic diamines is9,10-bis(4-aminophenyl)anthracene. Solvent-soluble positive-typephotosensitive polyimides containing 9,10-bis(4-aminophenyl)anthracenein the main chains are linear polymers having high mechanical strengthsand high moduli of elasticity, so that they are studied as highlyelastic polyimide fibers, and also as gas separation membranes becausethey can be made into films. They can be used as fibers or films, andalso as photosensitive films. Anthraquinone is easily photoexcited uponirradiation with light, so that it is widely used as a sensitizer. It ispresumed that 9,10-bis(4-aminophenyl)anthracene group is sensitized andactivated upon irradiation with light, and if a quinone diazide exists,it interacts with the acid generated by the photolysis of the quinonediazide, so that the aminophenyl groups on the 9- and 10-positions areattacked by the proton so as to be eliminated from the anthracene group,thereby generating anthraquinone. It is presumed that, as a result, thepolyimide is soluble in alkalis, so that clear positive-type images canbe formed. As can be seen from the fact that anthraquinone is known as asensitizer, the photosensitizing effect of this system is large, so thatit is not necessary to co-employ a separate sensitizer. Positive-typepatterns are effectively formed by irradiation of small energy for ashort time.

Additional preferred examples of the photosensitive aromatic diaminesare aromatic amines having biphenyl sulfone, such as3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone,bis-{4-(3-aminophenoxy)biphenyl}sulfone andbis{4-(4-aminophenoxy)biphenyl}sulfone. In this case, the biphenylsulfone are contained in the main chain of the polyimide. The polyimidescontaining biphenyl sulfone are linear polymers having high mechanicalstrengths and high moduli of elasticity, so that they are studied ashighly elastic polyimide fibers, and also as gas separation membranesbecause they can be made into films. They can be used as fibers orfilms, and also as photosensitive films. It was discovered as shown inthe Examples below, that they are soluble in alkalis by irradiation withlight after adding a quinone diazide compound. Even if the molecularweight (based on polystyrene) is changed to 40,000, 100,000 and 150,000,the polyimides are converted to be soluble in alkalis. From this fact,it is thought that the quinone diazide is photodecomposed to generate aradical and simultaneously to be converted to indene acid, and theyinteract with biphenyl sulfone photoexcited by irradiation with light soas to decompose the biphenyl sulfone to phenyl sulfonic acid, so thatthe polyimide is alkali-soluble. By UV irradiation, the quinone diazidecompound is photodecomposed and indene acid is further generated. It ispresumed that, as a result, the biphenyl group is activated and thesulfone bond is cleaved by the action of indene acid to produce phenylsulfonic acid, thereby increasing the solubility of the polyimide inalkalis.

Additional preferred examples of the photosensitive aromatic diaminesinclude bis{4-(4-aminophenoxy)phenyl}sulfone,bis{4-(3-aminophenoxy)phenyl}sulfone, o-tolidine sulfone,4,4′-diaminobenzophenone, 3,3′-diaminobenzophenone,2-nitro-1,4-diaminobenzene, 3,3′-dinitro-4,4′-diaminobiphenyl,3,3′-dimethoxy-4,4′-diaminobiphenyl and 1,5-diaminonaphthalene.

The above-mentioned various photosensitive aromatic diamines may beemployed individually or in combination.

By employing an aromatic diamine into which hydroxyl group, pyridinegroup, oxycarbonyl group or tertiary amine group is introduced(hereinafter also referred to as “alkali-solubility-increasing aromaticdiamine”), the aromatic diamine is bound to or interacts with the acidproduced by the photoacid generator, so that positive-type images aremore easily formed by alkali treatment.

As the preferred alkali-solubility-increasing aromatic diamines,firstly, diaminopyridine and diaminoacridinium are exemplified. Weaklybasic pyridine groups contained in the polyimide main chain formsacid-base bond with the acid generated by UV irradiation ofdiazonaphthoquinone so that the polyimide becomes soluble in alkalis.The diaminopyridine in the main chain of the polyimide may be2,6-diaminopyridine, 3,5-diaminopyridine,3,5-diamino-2,4-dimethylpyridine and the like. Preferably,2,6-diaminopyridine or 3,5-diaminopyridine is employed. As the compoundshaving pyridine ring, diaminoacridium may be used. For example,acriflavin, Acridine Yellow, proflavin and the like may be employed, andacriflavin is preferred.

Additional preferred examples of the alkali-solubility-increasingaromatic diamines are hydroxyl group-containing or alkoxylgroup-containing aromatic diamines which are diaminodihydroxybenzene,diaminodihydroxybiphenyl or diaminodialkoxybiphenyl. These hydroxylgroup-containing or alkoxyl group-containing aromatic diamines arepreferably contained as one component in the polyimide containing notless than two types of aromatic diamine components. Preferred examplesof these aromatic diamines include 1,4-diamino-2-hydroxybenzene,3,3′-dihydroxy-4,4′-diaminobiphenyl and3,3′-dimethoxy-4,4′-diaminobiphenyl. The hydroxyl groups and the methoxygroups in the polyimide main chain are bound to the acid produced by thelight irradiation of the quinone diazide so that the polyimide issoluble in alkalis.

Another preferred example of the alkali-solubility-increasing aromaticdiamines is 1,4-bis(3-aminopropyl)piperazine (hereinafter referred to as“diaminopiperazine”). This is preferably contained in the polyimide mainchain together with other aromatic diamine(s). The diaminopiperazinecontained in the polyimide main chain together with the aromaticdiamine(s) is a highly basic compound having two tertiary amines.Therefore, the piperazine group is bound to the carboxylic acidgenerated by light irradiation of the diazonaphthoquinone so as to formacid-base bond, so that the polyimide is soluble in alkalis.

Another preferred example of the alkali-solubility-increasing aromaticdiamines is 3,9-bis(3-aminopropyl)2,4,8,10tetraoxaspiro-(5,5)-undecane.This is preferably contained in the polyimide main chain together withother aromatic diamine(s). Diaminotetraoxaspiroundecane is known to bedecomposed by an acid to aldehyde and alcohol. It is presumed that thetetraoxaspiro group in the polyimide main chain of the polyimidecontaining diaminotetraoxaspiroundecane is decomposed by the action ofthe carboxylic acid generated by the light irradiation so that thepolyimide is soluble in alkalis, thereby the polyimide shows thecharacteristics of positive-type photosensitive photoresists.

Additional preferred examples of the alkali-solubility-increasingaromatic diamines are acid amides of diaminobenzoic acid. In this case,the polyimide main chain preferably contains not less than two types ofaromatic diamine components and one of them is acid amide ofdiaminobenzoic acid. Preferred examples of the acid amide ofdiaminobenzoic acid are morpholine amide and N-methylpiperazine amide of3,5-diaminobenzoic acid. However, the acid amide of diaminobenzoic acidis not restricted thereto, and aliphatic primary, secondary and tertiaryamines may be employed, and alcohols and aliphatic amines containingthese bases may also be employed. Here, the number of carbon atoms in“aliphatic amine” is not restricted, but about 2 to 6 is usuallypreferred.

Additional preferred examples of the alkali-solubility-increasingaromatic diamine are 3,5-diaminobenzoic acid and2-hydroxy-1,4-diaminobenzene.

The above-described various photosensitive diamines, may be employedindividually or in combination.

Use of the above-described photosensitive aromatic diamine and/oralkali-solubility-increasing aromatic diamine is not indispensable, andthe polyimides constituted by the combination of the above-mentioned oneor more aromatic diamine components and the one or more aromatic acidcomponents may be employed. Especially, in cases where electron beam isused for exposure, good positive-type images may be formed with highsensitivity even without using the photosensitive aromatic diamineand/or the alkali-solubility-increasing aromatic diamine.

The diamine component of the polyimide may be constituted by theabove-mentioned photosensitive aromatic diamine and/oralkali-solubility-increasing aromatic diamine alone, or the polyimidemay contain the photosensitive aromatic diamine and/oralkali-solubility-increasing aromatic diamine together with the one ormore of the above-described aromatic diamine components. The content ofthe photosensitive aromatic diamines and/or thealkali-solubility-increasing aromatic diamines based on the totalaromatic diamine components is preferably 30 to 100 mol %, morepreferably 50 to 100 mol %.

It should be noted that in the above-described various compounds andcomponents containing alkyl groups or the alkyl moiety-containinggroups, the number of carbon atoms in the alkyl groups or the alkylmoieties is preferably 1 to 6 unless otherwise specified. Further, asthe aromatic ring, unless otherwise specified, benzene ring, naphthalenering and anthracene ring as well as hetero rings of these rings arepreferred.

The polyimide in the composition according to the present invention issolvent-soluble. The term “solvent-soluble” means that the polyimide canbe dissolved in N-methyl-2-pyrrolidone (NMP) at a concentration of notless than 5% by weight, preferably not less than 10% by weight.

The polyimide in the composition according to the present inventionpreferably has a weight average molecular weight based on polystyrene of25,000 to 400,000, more preferably 30,000 to 200,000. If the weightaverage molecular weight is within the range of 25,000 to 400,000, goodsolubility in solvent good film-forming properties, high film strengthand high insulation may be attained. Further, in addition tosatisfaction of the above-mentioned range of the molecular weight, it ispreferred that the thermal decomposition initiation temperature be notlower than 450° C. from the view point of heat resistance.

The polyimide in the composition according to the present invention maybe produced by direct imidation reaction between the aromatic diamineand the aromatic tetracarboxylic dianhydride. In the production of theconventional negative-type polyimide photoresists, a polyamic acidhaving photoreactive side chains are used. The polyamic acid is easilydecomposed at room temperature, so that the storage stability is poor.Further, the photosensitive polyamic acid requires heat treatment at 250to 350° C. so as to carry out imidation reaction. In contrast, thepolyimide in the composition according to the present invention isdirectly produced by the imidation reaction between the aromatic diamineand the aromatic tetracarboxylic dianhydride in solution, but not apolyamic acid, so that the production process thereof is largelydifferent from that of the conventional negative-type polyimides.

The direct imidation reaction between the aromatic diamine and thearomatic tetracarboxylic dianhydride may be carried out using acatalytic system utilizing the following equilibrium reaction between alactone, base and water.

{lactone}+{base}+{water}={acid}⁺{base}⁻

A polyimide solution may be obtained by using the {acid}⁺{base}⁻ systemas a catalyst and heating the reaction mixture at 140-180° C. The waterproduced by the imidation reaction is eliminated from the reactionsystem by azeotropic distillation with toluene. When the imidation inthe reaction system is completed, {acid}⁺{base}⁻ is converted to thelactone and the base, and they lose the catalytic activity and areremoved from the reaction system. The polyimide solution produced bythis process can be industrially used as it is as a polyimide solutionwith high purity because the above-mentioned catalytic substances arenot contained in the polyimide solution after the reaction.

Examples of the reaction solvent which may be used in theabove-mentioned imidation reaction include, in addition to theabove-mentioned toluene, N-methyl-2-pyrrolidone, dimethylformamide,dimethylacetamide, dimethylsulfoxide, sulfolane, tetramethylurea and thelike.

As the lactone, γ-valerolactone is preferred. As the base, pyridineand/or methylmorpholine is(are) preferred.

The mixing ratio (acid/diamine) between the aromatic acid dianhydrideand the aromatic diamine subjected to the imidation reaction ispreferably about 1.05 to 0.95 in terms of molar ratio. Further, theconcentration of the acid dianhydride based on the total reactionmixture is preferably about 4 to 16% by weight, the concentration of thelactone is preferably about 0.2 to 0.6% by weight, the concentration ofthe base is preferably about 0.3 to 0.9% by weight, and theconcentration of the toluene is preferably about 6 to 15% by weight atthe initiation of the reaction. The reaction time is not restricted andvaries depending on the molecular weight of the polyimide to be producedand the like, and usually about 2 to 10 hours. It is preferred to carryout the reaction under stirring.

It should be noted that the production process per se of the polyimideusing the binary catalytic system comprising the lactone and the base isknown, and described in, for example, U.S. Pat. No. 5,502,143.

By carrying out the above-described imidation reaction sequentiality intwo steps using different acid dianhydrides and/or different diamines,polyimide block copolymers can be produced. By the conventional processfor producing polyimide through polyamic acid, only random copolymerscan be produced as copolymers. Since polyimide block copolymers can beproduced selecting arbitrary acids and/or diamines, desired propertiesor functions such as adhesiveness, dimensional stability, low dielectricconstant and the like can be given to the polyimide. In the compositionof the present invention, such a polyimide copolymer may also beemployed.

A preferred process for producing the polyimide block copolymers includethe process wherein a polyimide oligomer is produced using the acidcatalyst generated by the above-described lactone and the base, andusing either one of the aromatic diamine component or thetetracarboxylic dianhydride in excess, and then the aromatic diamineand/or the tetracarboxylic dianhydride is(are) added (the molar ratio ofthe total aromatic diamines to the total tetracarboxylic dianhydride is1.05 to 0.95), thereby carrying out two-step polycondensation.

The photosensitive polyimide composition according to the presentinvention preferably contains the photoacid generator in an amount of 10to 50% by weight based on the weight of the polyimide.

The photosensitive polyimide composition according to the presentinvention may be in the form of solution suited for application onsubstrates. In this case, as the solvent, a polar solvent such asN-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide,dimethylsulfoxide, sulfolane, tetramethylurea or the like; which is usedas the solvent for the imidation reaction, may be employed. Theconcentration of the polyimide in the solution may preferably be 5% to50% by weight, more preferably 10% to 40% by weight. Since the polyimideobtained by the direct imidation using the catalytic system comprisingthe lactone and the base is obtained in the form of solution in whichthe polyimide is dissolved in the polar solvent, and since theconcentration of the polyimide in the obtained solution is within thepreferred range mentioned above, the polyimide solution produced by theabove-described process may advantageously be used as it is. If desired,however, the produced polyimide solution may be diluted with diluent. Asthe diluent, a solvent which does not largely decrease the solubility,such as dioxane, dioxolane, γ-butyrolactone, cyclohexanone, propyleneglycol monomethyl ether acetate, methyl lactate, anisole, ethyl acetateor the like may be employed, although the diluent is not restricted tothese.

To make the composition of the present invention fitted to each finaluse, the sensitivity of the pattern resolution may be increased bygiving a photosensitizer to the photosensitive polyimide of the presentinvention. Although not restricted, examples of the photosensitizerinclude Michler's ketone, benzoin ether, 2-methylanthraquinone,benzophenone and the like. Further, modifiers which are added to theordinary photosensitive polyimides, such as coupling agents,plasticizers, film-forming resins, surfactants, stabilizers, spectrumsensitivity-adjusters and the like may be added.

By applying the photosensitive polyimide composition of the presentinvention in the form of solution on a substrate, drying thecomposition, selectively exposing the composition, and developing theresultant, a polyimide membrane having an arbitrary pattern on thesubstrate can be formed. Alternatively, by forming a polyimide film fromthe polyimide composition by a conventional method such as extrusion,adhering the film on a substrate, selectively exposing the film anddeveloping the resultant, a polyimide membrane having an arbitrarydesired pattern on the substrate may be formed. Since such a polyimidemembrane is resistant to heat and insulative, it may be used as aninsulation membrane or dielectric layer in semiconductor devices as itis. Alternatively, it may be used as a photoresist for selectivelyexposing the substrate.

Examples of the substrate to which the photosensitive polyimide of thepresent invention is applied include semiconductor disks, siliconwafers, germanium, gallium arsenide, glass, ceramics, copper foil,printed boards and the like.

Coating of the composition may be carried out usually by dipping,spraying, roll coating, spin coating or the like. As for the adhesivefilms, products having uniform thickness may be usually obtained byemploying thermocompression bonding. By employing these methods, thephotosensitive polyimide according to the present invention may beeffectively used for forming coating layers with a thickness of 0.1 to200 μm, or for forming relief structures.

The thin membranes in multilayered circuits used as temporaryphotoresists or as insulation layers or dielectric layers may preferablyhave a thickness of about 0.1 to 5 μm. In cases where the membrane isused as a thick layer such as immobile layer, the thickness thereof maypreferably be 10 to 200 μm in order to protect the semiconductormemories from α-ray.

It is preferred to carry out preheating at a temperature of 80 to 120°C. after applying the photosensitive polyimide to the substrate. In thiscase, an oven or heating plate is used, and an infrared heater ispreferably employed as the heater. The drying time in this case may beabout 5 to 20 minutes.

Thereafter, the photosensitive polyimide layer is subjected toirradiation. Usually, UV light is used, but high energy radiation, suchas X-ray, electron beam or high power oscillation beam from anextra-high pressure mercury lamp may be employed. Although irradiationor exposure is carried out through a mask, the surface of thephotosensitive polyimide layer may also be irradiated withthe radiationbeam. Usually, irradiation is carried out using a UV lamp which emits alight having a wavelength of 250 to 450 nm, preferably 300 to 400 nm.The exposure may be carried out using a single color ray or multiplecolor rays. It is preferred to use a commercially available irradiationapparatus, such as contact and interlayer exposing apparatus, scanningprojector or wafer stepper.

After the exposure, by treating the photosensitive layer with adeveloper which is an aqueous alkaline solution, the irradiated regionsof the photoresist layer can be removed, thereby a pattern is obtained.The treatment may carried out by dipping the photoresist layer orspraying the developer under, pressure to the photoresist layer so as todissolve the exposed regions of the substrate. Examples of the alkali tobe used as the developer include, although not restricted, aminoalcoholssuch as aminoethanol, methyl morpholine, potassium hydroxide, sodiumhydroxide, sodium carbonate, dimethylaminoethanol, hydroxytetramethylammonium and the like. Although the concentration of the alkali in thedeveloper is not restricted, it is usually about 30 to 5% by weight.

The development time varies depending on the energy of exposure,strength of the developer, manner of development, preheatingtemperature, temperature of the treatment with the developer and thelike. Usually, with the development by dipping, the development time isabout 1 to 10 minutes, and with the development by spraying, thedevelopment time is usually about 10 to 60 seconds. The development isstopped by dipping the developed layer in an inactive solvent such asisopropanol or deionized water, or by spraying such a solvent.

By using the positive-type photosensitive polyimide compositionaccording to the present invention, polyimide coating layers having alayer thickness of 0.5 to 200 μm, and relief structures having sharpedges may be formed.

Since the polyimide in the composition of the present invention iscomposed of complete linear polyimide, it is not changed in water orheating, and its storage stability is good. Therefore, it can be used asphotosensitive films. Further, after forming the pattern by development,unlike the polyamic acid molecules, the postbake at 250 to 450° C. isnot necessary, and only drying under heat at 120 to 200° C. to evaporatethe solvent is carried out. Further, the polyimide membrane afterforming the pattern is tough, resistant to high temperature andexcellent in mechanical properties.

As for the photoresists comprising a novolak photosensitive material anda diazonaphthoquinone, it is said that both the resolution andsensitivity are excellent when the molecular′weight of the novolak isnot more than 10,000, and is uniformed within the range of 5000 to10,000.

Similarly, the resolution and photosensitivity of the positive-typephotosensitive polyimides, as well as the heat resistance, chemicalresistance and mechanical strength, are variable depending on themolecular weight and the molecular weight distribution. There is atendency that the larger the molecular weight and the smaller thecarboxylic acid content, the longer the development time and the dippingtime in the alkali solution.

The present invention will now be described more concretely by way ofexamples. It should be noted, however, the following examples arepresented for the illustration purpose only and should not beinterpreted in any restrictive way. It is apparent for those skilled inthe art that photosensitive polyimides having various characteristicsare obtained by combination of various acid dianhydrides and aromaticdiamines.

EXAMPLE 1

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap. To this flask,22.21 g (50 mmol) of4,4′-{2,2,2-trifluoro-1-(trifluoromethyl)ethylidene}bis(1,2-benzenedicarboxylicdianhydride) (commercial product of Hoechst-Celanese, molecular weight:444.25, hereinafter referred to as “6FDA”), 25.93 g (50 mmol) of2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane (hereinafter referredto as “HFBAPP”), 1.0 g (10 mmol) of γ-valerolactone, 1.6 g (20 mmol) ofpyridine, 185 g of N-methylpyrrolidone, and 30 g of toluene were added.After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 0.5 hours, the mixture was heated at 180° C. and stirredat 180 rpm for 2.0 hours. In the reaction, toluene-water azeotrope wasremoved.

The polymer concentration thus obtained was 20% by weight. The molecularweight of this polyimide was measured by high performance liquidchromatography (produced by Tosoh Corporation). The molecular weightsbased on polystyrene were: Number Average Molecular Weight (Mn): 57,800;Weight Average Molecular Weight (Mw): 108,100; Z Average MolecularWeight (Mz): 192,300; Mw/Mn=1.87; Mz/Mn=3.33. More particularly, themolecular weights were measured as follows: That is, the molecularweights were measured by using high performance liquid chromatographyproduced by Tosoh Corporation. As the developing solution,LiBr-containing dimethylformamide was used. The molecular weight interms of styrene was measured, and the number average molecular weight(Mn), weight average molecular weight (Mw), Z average molecular weight(Mz), Mw/Mn ratio and Mz/Mn ratio were measured.

EXAMPLE 2

The procedure was run the same way as Example 1.

To the separable three-necked flask, 14.71 g (50 mmol) of3,4,3′,4′-biphenyltetracarboxylic dianhydride (commercial product of UbeIndustries, Ltd., hereinafter referred to as “BPDA”), 5.00 g (25 mmol)of 2,3-diaminodiphenyl ether, 10.27 g (25 mmol) of2,2-bis{4-(4-aminophenoxy)phenyl}propane (hereinafter referred to as“BAPP”), 0.5 g of γ-valerolactone (5 mmol), 0.8 g (10 mmol) of pyridine,113 g of N-methylpyrrolidone and 30 g of toluene were added. Afterstirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 0.5 hours, the mixture was heated at 180° C. and stirredat 180 rpm for 0.5 hours. In the reaction, toluene-water azeotrope wasremoved.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 26,000; Weight Average Molecular Weight(Mw): 42,900; Z Average Molecular Weight (Mz): 60,800; Mw/Mn=1.65;Mz/Mn=2.33.

EXAMPLE 3

The procedure was run the same way as Example 1.

To the separable three-necked flask, 8.89 g (20 mol) of 6FDA, 5.19 g (10mmol) of HFBAPP, 0.3 g (3 mmol) of γ-valerolactone, 0.5 g (6 mmol) ofpyridine, 70 g of N-methylpyrrolidone and 20 g of toluene were added.After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 0.5 hours, the mixture was heated at 180° C. and stirredat 180 rpm for 1 hour. In the reaction, toluene-water azeotrope wasremoved.

After cooling at room temperature, 2.94 g (10 mmol) of BPDA, 6.40 g (20mmol) of 2,2′-bis(trifluoromethyl-benzidine), 57 g ofN-methylpyrrolidone and 10 g of toluene were added and the mixture wasstirred at room temperature for 1 hour, followed by stirring the mixtureat 180° C. at 180 rpm for 3.75 hours. In the reaction, toluene-waterazeotrope was removed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 24,800; Weight Average Molecular Weight(Mw): 41,700; Z Average Molecular Weight (Mz): 63,300; Mw/Mn=1.68;Mz/Mn=2.65.

EXAMPLE 4

The procedure was run the same way as Example 3.

To the separable three-necked flask, 9.67 g (30 mmol) of3,4,3′,4′-benzophenone tetracarboxylic dianhydride (hereinafter referredto as “BTDA”), 4.89 g (40 mmol) of 2,4-diaminotoluene, 8,80 g (10 mmol)of diaminosiloxane (commercial product of Shin-etsu Chemical Co., Ltd.,amine value: 440), 1.0 g (10 mmol) of γ-valerolactone, 1.6 g (20 mmol)of pyridine, 60 g of N-methylpyrrolidone and 30 g of toluene were added.After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 0.5 hours, the mixture was heated at 180° C. and stirredat 180 rpm for 1 hour. In the reaction, toluene-water azeotrope wasremoved.

After cooling at room temperature, 14.71 g (50 mmol) of BPDA, 4.00 g (20mmol) of 3,4′-diaminodiphenyl ether, 4.105 g (10 mmol) of BAPP, 70 g ofN-methylpyrrolidone and 30 g of toluene were added and the mixture wasstirred at room temperature for 25 minutes, followed by stirring themixture at 180° C. at 180 rpm for 4 hours. After the reaction, 43 g ofN-methylpyrrolidone was added.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 31,700, Weight Average Molecular Weight(Mw): 56,400; Z Average Molecular Weight (Mz): 88,900; Mw/Mn=1.78;Mz/Mn=2.81.

EXAMPLE 5 Preparation of Photosensitive Composition and Formation ofPattern by Selective Exposure

(1) Preparation of Photosensitive Composition

Photosensitive compositions were prepared by mixing the components shownin Table 1 below and filtering the mixture through a filter having 3 μmdiameter of pores.

TABLE 1 Composition Components I II III IV Polyimide Solution Example 1Example 2 Example 3 Example 4 Weight 15 g 15 g 20 g 15 g (PolyimideContent)  3 g  3 g  3 g  3 g 1,2-naphthoquinone-2- 0.9 g  0.9 g  0.9 g 0.9 g  diazide-5-sulfonic acid-o- cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions was spin-coatedon 5 cm diameter of surface-treated copper foil (commercial product ofNippon Denkai, 18 μm thickness). Thereafter, photosensitive layer wasdried at 90° C. for 10 minutes in an infrared light oven. The thicknessof this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) was placed, and the photosensitvelayer was irradiated at a dose of exposure at which images are obtainedusing 2 kW extra-high pressure mercury lamp apparatus (JP-2000G,commercial product of Oak Seisakusho). The wavelength range was 320 to390 nm and the peak was 360 nm (these conditions were consistent in thefollowing examples too). The dose of UV light and the developing timeare shown in Table 2 below.

TABLE 2 Composition I II III IV Dose of UV Light (mJ) 1000 500 1000 1000Developing Time (minutes) 25 5 3 7

The developer was a mixture of 30 g of aminoethanol, 30 g ofN-methylpyrrolidone and 30 g of water. The photosensitive layer afterthe irradiation was dipped in the developer for the above-described timeperiod, washed with deionized water, dried with an infrared oven, andthe resolution was observed. The thickness of this polyimidephotosensitive layer after drying at 90° C. for 30 minutes was about 9μm.

With all of the compositions I, II, III and IV, as for the through holepatterns in the photosensitive layer, formation of through holes havingsharp and circular sections having a diameter of 15 μm was confirmed. Asfor the line-and-space pattern, formation of images of lines having awidth of 15 μm was confirmed.

EXAMPLE 6

The procedure was run the same way as Example 1.

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap.

17.77 g (40 mmol) of 6FDA, 8.65 g (20 mmol) of M-BAPS, 4.25 g (20 mmol)of 3,3′-dimethylbenzidine, 0.4 g (4 mmol) of γ-valerolactone, 0.6 g (8mmol) of pyridine, 117 g of N-methylpyrrolidone and 30 g of toluene wereadded. After stirring the mixture at 180 rpm at room temperature undernitrogen atmosphere for 0.5 hours, the mixture was heated at 180° C. andstirred at 180 rpm for 4.75 hours. In the reaction, toluene-waterazeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 67,300; Weight Average Molecular Weight(Mw): 128,300; Z Average Molecular Weight (Mz): 219,500; Mw/Mn=1.90;Mz/Mn=3.26.

EXAMPLE 7

The procedure was run the same way as Example 6.

To the separable three-necked flask, 13.09 g (60 mmol) of pyromelliticdianhydride, 14.89 g (60 mmol) ofbicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride(hereinafter referred to as “BCD”), 61.9 g (120 mmol) of m-BAPS, 1.2 g(12 mmol) of γ-valerolactone, 1.2 g (24 mmol) of pyridine, 302 g ofN-methylpyrrolidone and 50 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 0.5hours, the mixture was heated at 180° C. and stirred at 180 rpm for 3.75hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 71,100; Weight Average Molecular Weight(Mw): 113,600; Z Average Molecular Weight (Mz): 167,100; Mw/Mn=1.60;Mz/Mn=2.35.

EXAMPLE 8

The procedure was run as the same way as Example 3.

To the separable three-necked flask, 9.67 g (3.0 mol) of BTDA, 9.13 g(60 mmol) of 3,5-diaminobenzoic acid, 1.2 g (12 mmol) ofγ-valerolactone, 2.4 g (24 mmol) of pyridine, 150 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 0.5hours, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. In the reaction, toluene-water azeotrope was removed. Aftercooling at room temperature, 29.00 g (90 mmol) of BPDA, 12.98 g (30mmol) of m-BAPS, 10.46 g (30 mmol) of 9;9-bis(4-aminophenyl)fluorene,118 g of N-methylpyrrolidone and 20 g of toluene were added and themixture was stirred at room temperature for 0.45 hours, followed bystirring the mixture at 180° C. at 180 rpm for 2.60 hours. In thereaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 29,900; Weight Average Molecular Weight(Mw): 77,400; Z Average Molecular Weight (Mz): 175,400; Mw/Mn=2.59;Mz/Mn=5.86.

EXAMPLE 9

The procedure was run the same way as Example 3.

To the separable three-necked flask, 12.89 g (40 mol) of BTDA, 8.65 g(20 mmol) of m-BAPS, 0.4 g (4 mmol) of γ-valerolactone, 0.64 g (8 mmol)of pyridine, 77 g of N-methylpyrrolidone and 30 g of toluene were added.After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 0.5 hours, the mixture was heated at 180° C. and stirredat 180 rpm for 1 hour. In the reaction, toluene-water azeotrope wasremoved. After cooling the resultant to room temperature, 2.16 g (10mmol) of 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2.00 g (10 mmol) of3,4′-diaminodiphenyl ether, 20 g of N-methylpyrrolidone and 10 g oftoluene were added and the mixture was stirred at room temperature for0.45 hours, followed by stirring the mixture at 180° C. at 180 rpm for1.0 hour. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 32,300; Weight Average Molecular Weight(Mw): 140,200; Z Average Molecular Weight (Mz): 442,000; Mw/Mn=4.34;Mz/Mn=13.68.

EXAMPLE 10

The procedure was run the same way as Example 5.

(1) Preparation of Photosensitive Composition

Photosensitive compositions were prepared by mixing the components shownin Table 3 below and filtering the mixture through a filter having 3 μmdiameter of pores.

TABLE 3 Composition Components V VI VII Polyimide Solution Example 7Example 8 Example 9 Weight 15 g 20 g 15 g (Polyimide Content)  3 g  3 g 3 g 1,2-naphthoquinone-2- 0.9 g  0.9 g  0.9 g  diazide-5-sulfonicacid-o- cresol ester

(2) Method of Formation of Images

Each of the above-described photosensitive compositions was spin-coatedon 5 cm diameter of a surface of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thephotosensitive layer was dried at 90° C. for 10 minutes in an infraredoven. The thickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) was placed, and the photosensitivelayer was irradiated at a dose of exposure at which images are obtainedusing 2 kW extra-high pressure mercury lamp apparatus (JP-2000G,commercial product of Oak Seisakusho). The dose of UV light and thedeveloping time are shown in Table 4 below.

TABLE 4 Composition V VI VII Dose of UV Light (mJ) 500 500 500Developing Time (minutes) 15 8 8

The developer was a mixture of 30 g of aminoethanol, 70 g ofN-methylpyrrolidone and 30 g of water.

The photosensitive layer after the irradiation was dipped in thisdeveloper for the above-described time period, washed with deionizedwater, dried with an infrared lamp, and the resolution was observed. Thethickness of this polyimide layer after drying at 90° C. for 30 minuteswas about 9 μm.

With all of the compositions V, VI and VII, as for the through holepatterns in polyimide photosensitve layer, formation of through holeshaving sharp and circular sections having a diameter of 15 μm wasconfirmed. As for the line-and-space pattern, formation of images oflines having a width of 15 μm was confirmed.

EXAMPLE 11

The procedure was run the same way as Example 3.

To the separable three-necked flask, 19.33 g (60 mmol) of BTDA, 14.97 g(90 mmol) of 4,4′-diaminodiphenyl sulfide, 1.5 g (15 mmol) ofγ-valerolactone, 2.4 g (30 mmol) of pyridine, 150 g ofN-methylpyrrolidone and 30 g of toluene were added.

After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 0.5 hours, the mixture was heated at 180° C. and stirredat 180 rpm for 1 hour. After the reaction, toluene-water azeotrope wasremoved.

After cooling the resultant to room temperature, 26.48 g (90 mmol) ofBPDA, 6.4 g (30 mmol) of 3,3′-dihydroxybenzidine, 12.98 g (30 mmol) ofm-BAPS, 85 g of N-methylpyrrolidone and 30 g of toluene were added andthe mixture was stirred at room temperature for 25 minutes, followed bystirring the mixture at 180° C. at 180 rpm for 2 hours. After thereaction, 79 g of N-methylpyrrolidone was added.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 24,000; Weight Average Molecular Weight(Mw): 48,500; Z Average Molecular Weight (Mz): 82,100; Mw/Mn=2.02;Mz/Mn=3.41.

EXAMPLE 12

The procedure was run the same way as Example 3.

To the separable three-necked flask, 9.67 g (30 mol) of BTDA, 9.13 g (60mmol) of 3,5-diaminobenzoic acid, 1.2 g (12 mmol) of γ-valerolactone,2.0 g (24 mmol) of pyridine, 150 g of N-methylpyrrolidone and 30 g oftoluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 0.5 hours, the mixture washeated at 180° C. and stirred at 180 rpm for 1 hour. After the reaction,toluene-water azeotrope was removed.

After cooling at room temperature, 29.00 g (90 mmol) of BTDA, 12.98 g(30 mmol) of m-BAPS, 6.49 g (30 mmol) of 3,3′-dihydroxybenzidine, 102 gof N-methylpyrrolidone and 20 g of toluene were added and the mixturewas stirred at room temperature for 0.45 hours, followed by stirring themixture at 180° C. at 180 rpm for 2.50 hours. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example were: Number AverageMolecular Weight (Mn): 24,000; Weight Average Molecular Weight (Mw):45,700; Z Average Molecular Weight (Mz): 82,300; Mw/Mn=1.90; Mz/Mn=3.42.

EXAMPLE 13

The procedure was run the same way as Example 12.

To the separable three-necked flask, 2.18 g (10 mmol) of pyromelliticdianhydride, 6.40 g (20 mmol) of 2,2′-di-trifluoromethyl-benzidine, 0.4g (4 mmol) of γ-valerolactone, 0.8 g (10 mmol) of pyridine, 86 g ofN-methylpyrrolidone and 20 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 0.5hours, the mixture was heated at 180° C. and stirred at 180 rpm for 1.0hour. After the reaction, toluene-water azeotrope was removed.

After cooling at room temperature, 8.83 g (30 mmol) of BPDA, 4.79 g(11.67 mmol) of BAPP, 1.52 g (10 mmol) of 3,5-diaminobenzoic acid, 30 gof N-methylpyrrolidone and 10 g of toluene were added and the mixturewas stirred at room temperature for 0.5 hours, followed by stirring themixture at 180° C. at 180 rpm for 3 hours. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 17,800; Weight Average Molecular Weight(Mw): 31,100; Z Average Molecular Weight (Mz): 48,200; Mw/Mn=1.74;Mz/Mn=2.70.

EXAMPLE 14

The procedure was run the same way as Example 3.

To the separable three-necked flask, 2.94 g (10 mol) of BPDA, 6.40 g (20mmol) of 2,2′-di-trifluoromethyl-benzidine, 0.3 g (3 mmol) ofγ-valerolactone, 0.48 g (6 mmol) of pyridine, 78 g ofN-methylpyrrolidone and 20 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 0.5hours, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. After the reaction, toluene-water azeotrope was removed.

After cooling at room temperature, 5.88 g (20 mmol) of BPDA, 2.74 g(6.67 mmol) of BAPP, 0.76 g (5 mmol) of 3,5-diaminobenzoic acid, 20 g ofN-methylpyrrolidone and 10 g of toluene were added and the mixture wasstirred at room temperature for 0.5 hours. Then 0.33 g (3.33 mmol) ofmaleic anhydride and 10 g of N-methylpyrrolidone were added and themixture was stirred at room temperature for 0.5 hours, followed bystirring the mixture at 180° C. at 180 rpm for 3 hours. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 17,000; Weight Average Molecular Weight(Mw): 28,000; Z Average Molecular Weight (Mz): 42,300; Mw/Mn=1.54;Mz/Mn=2.48.

EXAMPLE 15

Operations basically similar to those in Example 5 were carried out.

(1) Preparation of Photosensitive Composition

Photosensitive compositions were prepared by mixing the components shownin Table 5 below and filtering the mixture through a filter having 3 μmdiameter of pores.

TABLE 5 Composition Components VIII IX X XI Polyimide Example 11 Example12 Example 13 Example 14 Solution Weight 15 g 15 g 20 g 15 g (Polyimide 3 g  3 g  3 g  3 g Content) 1,2-naphtho- 0.9 g  0.9 g  0.9 g  0.9 g quinone- 2-diazide- 5-sulfonic acid- o-cresol ester

(2) Method of Formation of Images

Each of the above-described photosensitive compositions was spin-coatedon 5 cm diameter of surface-treated copper foil (commercial product ofNippon Denkai, 18 μm thickness). Thereafter, the photosensitive layerwas dried at 90° C. for 10 minutes in an infrared oven. The thickness ofthis photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) was placed, and the photosensitivelayer was irradiated at a dose of exposure at which images are obtainedusing 2 kW extra-high pressure mercury lamp apparatus (JP-2000G,commercial product of Oak Seisakusho). The dose of UV light and thedeveloping time are shown in Table 6 below.

TABLE 6 Composition VIII IX X XI Dose of UV Light (mJ) 500 500 500 700Developing Time (minutes) 1 1 5 11

The developer was a mixture of 30 g of aminoethanol, 30 g ofN-methylpyrrolidone and 30 g of water.

The photosensitive layer after the irradiation was dipped in thissolution for the above-described period, washed with deionized water,dried with an infrared lamp, and the resolution was observed. Thethickness of this polyimide layer after drying at 90° C. for 30 minuteswas about 9 μm.

With all of the compositions VIII, IX, X and XI, as for the through holepatterns in the polyimide photosensitive layer, formation of throughholes having sharp and circular sections having a diameter of 15 μm wasconfirmed. As for the line-and-space pattern, formation of images oflines having a width of 15 μm was confirmed.

EXAMPLE 16

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap. While dippingthe flask in a silicone bath to heat the flask under stirring and undernitrogen gas flow, 32.23 g (1.00 mol) of 3,4,3′,4′-benzophenonetetracarboxylic dianhydride (commercial product of Himie Linz Ges.m.b.H, Molecular Weight: 322.23, hereinafter referred to as “BTDA”),21.63 g (50 mmol) of bis-4-(3-aminophenoxy)phenylsulfone (commercialproduct of Wakayama Seika Co., Ltd., Molecular Weight: 432.5), 13.27 g(50 mmol) of 3,3′-diamino-4,4′-dimethylbiphenylsulfone (commercialproduct of Wakayama Seika Co., Ltd., Molecular Weight: 274.3,hereinafter referred to as “o-tolidine sulfone”), 1.0 g (10 mmol) ofγ-valerolactone, 1.6 g (20 mmol) of pyridine, 257 g ofN-methylpyrrolidone and 60 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. (the bath temperature) andstirred at 180 rpm for 4.5 hours. The reaction completed while removingthe toluene-water azeotrope (14 ml).

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 26,760; Weight Average Molecular Weight(Mw): 39,540; Z Average Molecular Weight (Mz): 57,160; Mw/Mn=1.48. Thispolyimide was poured into methanol to convert it to powders which weresubjected to thermal analysis. The thermal decomposition temperature ofthe polyimide was 484° C.

EXAMPLE 17

The procedure was run the same way as Example 16.

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap. While heatingthe flask under nitrogen gas flow and under stirring, 17.77 g (40 mmol)of 6FDA (commercial product of Hoechst-Celanese), 8.65 g (20 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone, 5.49 g (20 mmol) of o-tolidinesulfone, 0.5 g (5 mmol) of γ-valerolactone, 0.8 g (10 mmol) of pyridine,122 g of N-methylpyrrolidone and 30 g of toluene were added. Afterstirring the mixture at 200 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. and stirredat 180 rpm for 6.15 hours. In the reaction, toluene-water azeotrope wasremoved.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 66,590; Weight Average Molecular Weight(Mw): 102,450; Z.Average Molecular Weight (Mz): 148,540; Mw/Mn=1.54.This polyimide was poured into methanol to convert it to powders whichwere subjected to thermal analysis. The thermal decompositiontemperature of the polyimide was 431° C. and 506° C.

EXAMPLE 18

The procedure was run the same way as Example 16.

While heating the flask under nitrogen gas flow and under stirring,17.77 g (40 mmol) of 6FDA, 8.21 g (20 mmol) of2,2-bis-4(4′-aminophenoxy)phenylpropane (commercial product of WakayamaSeika Co., Ltd., Molecular Weight: 410.5), 5.49 (20 mmol) of o-tolidinesulfone, 0.5 g (5 mmol) of γ-valerolactone, 0.8 g (10 mmol) of pyridine,120 g of N-methylpyrrolidone and 30 g of toluene were added in theflask.

After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. and stirredat 180 rpm for 3.15 hours. In the reaction, toluene-water azeotrope wasremoved.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 54,400; Weight Average Molecular Weight(Mw): 74,800; Z Average Molecular Weight (Mz): 100,200; Mw/Mn=1.37.

EXAMPLE 19

(1) Preparation of Photosensitive Composition

Photosensitive compositions were prepared by mixing the components shownin Table 7 below and filtering the mixture through a filter having 3 μmdiameter of pores.

TABLE 7 Composition Components XII XIII XIV Polyimide Solution Example16 Example 17 Example 18 Weight 15 g 15 g 15 g (Polyimide Content)  3 g 3 g  3 g naphthoquinonediazide- 0.9 g  0.9 g  0.9 g  1,2,5-o-cresolester

(2) Method of Formation of Images

Each of the above-described photosensitive compositions XII, XIII andXIV was spin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thephotosensitive layer was dried at 90° C. for 10 minutes in an infraredoven. The thickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) was placed, and the photosensitivelayer was irradiated at a dose of exposure at which images are obtainedusing 2 kW extra-high pressure mercury lamp apparatus (JP-2000G,commercial product of Oak Seisakusho).

The composition XII was irradiated with an energy of 300 mJ and thendeveloped under the following conditions. The developer was a mixture of40 g of N-methylpyrrolidone, 25 g of aminoethanol, 25 g of methanol and10 g of water. The photosensitive layer after the irradiation was dippedin this solution for 5 minutes, washed with deionized water, dried withan infrared lamp, and the resolution was observed. The thickness of thispolyimide photosensitive layer after drying at 90° C. for 30 minutes wasabout 9 μm.

As for the through hole patterns in the polyimide photosensitive layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

This polyimide photosensitive layer was heated with infrared oven at150° C. for 30 minutes. After this heat treatment, the thickness of thephotosensitive layer was 8 μm, so that the thickness was notsubstantially changed. The polyimide photosensitive layer was thenheated with infrared oven at 260° C. for 30 minutes, and the thicknessof the layer 6 μm.

The adhesion between the polyimide layer and the copper foil wasevaluated by cross cut test. The coating layer was cross cut with aknife such that each lattice had a size of 1 mm×1 mm and was tried topeeled off with a cellophane-tape. As a result, 100/100 latticesremained adhered (no lattices peeled off), so that the adhesion betweenthe polyimide layer and the copper foil was sufficiently high, which canbe used in practice.

The thermal decomposition temperature of this polyimide membrane was484° C., so that it showed good heat resistance in the high temperaturerange.

EXAMPLE 20

Operations basically similar to those in Example 4 were carried out.

The composition XIII was irradiated with an energy of 500 mJ and thendeveloped under the following conditions. The developer was a mixture of40 g of N-methylpyrrolidone, 25 g of aminoethanol, 25 g of methanol and10 g of water. The photosensitive layer after the irradiation was dippedin this solution for 2 minutes, washed with deionized water, dried withan infrared lamp, and the resolution was observed. The thickness of thispolyimide layer after drying at 90° C. for 30 minutes was about 20 μm.

As for the through hole patterns in the polyimide photosensitive layer,formation of through holes having sharp and circular sections having adiameter of 20 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 21

Operations basically similar to those in Example 4 were carried out.

The composition XIV was irradiated with an energy of 300 mJ and thendeveloped under the following conditions. The developer was a mixture of40 g of N-methylpyrrolidone, 25 g of aminoethanol, 25 g of methanol and10 g of water. The photosensitive layer after the irradiation was dippedin this solution for 3 minutes, washed with deionized water, dried withan infrared lamp, and the resolution was observed. The thickness of thispolyimide layer after drying at 90° C. for 30 minutes was about 11 μm.

As for the through hole patterns in the photosensitive polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

COMPARATIVE EXAMPLE 1

To 25 g of the polyimide solution (polyimide 5 g) of Example 16, 1.5 gof Michler's ketone was added and the resultant was mixed with a mixer.The mixture was coated on a copper foil by spin coating to a thicknessof about 10 μm after drying. The coated layer was irradiated in thesimilar manner as in Example 19. Images were not formed by irradiationof 500 mJ. Images were slightly formed by irradiation of 2500 mJ.

COMPARATIVE EXAMPLE 2

To 25 g of the polyimide solution (polyimide 5 g) of Example 16, 0.5 gof 2,6-bis(azidebenzylidene)4-methylcylohexanone and 1.5 g of Michler'sketone were added and the resultant was mixed with a mixer. The mixturewas coated on a copper foil by spin coating to 10 μm of thickness afterdrying. The coated layer was irradiated in the similar manner as inExample 19. Posi-typed images were not formed by irradiation of 2500 mJ.

EXAMPLE 22

In 25 g of the polyimide solution (polyimide 5 g) of Example 16, 1.5 gof Michler's ketone and 1.5 of naphthoquinone diazide-1,2,5-o-cresolester were added and the resultant was mixed with a mixer. The mixturewas coated on a copper foil by spin coating to 10 μm of thickness afterdrying. The coated layer was irradiated in the similar manner as inExample 19. Sensitive images were obtained by irradiation of 300 mJ.

EXAMPLE 23

In 25 g of the polyimide solution (polyimide 5 g) of Example 16, 1.5 gof naphthoquinone diazide-1,2,5-o-cresol ester was added and was mixedwith a mixer to obtain a uniform solution. As in Example 19, the mixturewas coated on a copper foil by spin coating to 10 μm of thickness afterdrying. The resulting polyimide layer was dried at 90° C. for 10 minutesand then irradiated with UV light of 300 mJ, immediately followed bytreatment with a developer. As a result, in about 30 seconds, imagesemerged, and the polyimide layer was washed with water. After drying,the polyimide layer was treated at 150° C. for 30 minutes. In thethrough hole test, although formation of holes with a diameter of 20 μmwas confirmed, the sharpness of the holes was poor.

On the other hand, after irradiation with light, the coated layer washeated at 150° C. for 10 minutes in an infrared oven, developed andheated at 150° C. for 30 minutes. Then the polyimide layer was treatedwith the developer for 5 minutes and then washed with water. With apositive-type test mask, formation of holes with a diameter of 15 μm wasconfirmed, but formation of holes with a diameter of 10 μm was notconfirmed. When a negative-type test mask was used, the regionscorresponding to the holes were observed as sharp projections with adiameter of 10 μm, so that formation of images of 10 μm size wasconfirmed.

EXAMPLE 24

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap. While heatingthe flask under nitrogen gas flow and under stirring, 17.77 g (40 mmol)of 6FDA (commercial product of Hoechst-Celanese), 8.65 g (20 mmol) ofm-BAPS, 6.97 g (20 mmol) of 9,9-bis(4-aminophenyl)fluorene (commercialproduct of Wakayama Seika Co., Ltd., hereinafter referred to as “FDA”),0.4 g (4 mmol) of γ-valerolactone., 0.6 g (8 mmol) of pyridine, 128 g ofN-methylpyrrolidone and 30 g of toluene were added in the flask. Afterstirring the mixture at 200 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. and stirredat 180 rpm for 5.85 hours. In the reaction, toluene-water azeotrope wasremoved.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 49,700; Weight Average Molecular Weight(Mw): 85,200; Z Average Molecular Weight (Mz): 123,000; Mw/Mn=1.71. Thispolyimide was poured into methanol to convert it to powders which weresubjected to thermal analysis. The thermal decomposition temperature ofthe polyimide was 540° C.

EXAMPLE 25

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 15 g (polyimidecontent: 3 g) of the polyimide solution obtained in Example 24 and 0.9 gof 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester, andfiltering the mixture through a filter having 3 μm diameter of pores.

(2) Formation of Images

The above-described photosensitive composition was spin-coated on 5 cmof diameter of surface-treated copper foil (commercial product of NipponDenkai, 18 μm thickness). Thereafter, the coated layer was dried at 90°C. for 10 minutes in an infrared oven. The thickness of thisphotosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) was placed, and the coating layerwas irradiated at a dose of exposure at which images are obtained using2 kW extra-high pressure mercury lamp apparatus (JP-2000G, commercialproduct of Oak Seisakusho).

The photosensitive layer was irradiated with an energy of 300 mJ andthen developed under the following conditions. The developer was amixture of 40 g of N-methylpyrrolidone, 25 g of aminoethanol, 25 g ofmethanol and 10 g of water. The coating layer after the irradiation wasdipped in this solution for 1 minute and 25 seconds, washed withdeionized water, dried with an infrared lamp, and the resolution wasobserved. The thickness of this polyimide layer after drying at 90° C.for 30 minutes was about 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

COMPARATIVE EXAMPLE 3

In 15 g of the polyimide solution obtained in Example 24, 0.9 g ofMichler's ketone was added and the mixture was well mixed to obtain auniform solution. The composition was irradiated with UV light of 2500mJ, and then treated in the same manner as in Example 25, but imageswere not obtained.

COMPARATIVE EXAMPLE 4

In 15 g of the polyimide solution obtained in Example 24, 0.9 g ofMichler's ketone and 0.3 g of2,6-bis(4-azidebenzilidene)-4-methylcyclohexanone were added and themixture was well mixed to obtain a uniform solution. The composition wasirradiated with UV light of 2500 mJ, and then treated in the same manneras in Example 25, but posi-typed images were not obtained.

EXAMPLE 26

The procedure was run the same way as Example 24.

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap. While heatingthe flask under nitrogen gas flow and under stirring, 12.89 g (40 mol)of BTDA, 8.65 g (20 mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 6.97g (20 mmol) of 9,9-bis(4-aminophenyl)fluorene, 0.4 g (4 mmol) ofγ-valerolactone, 0.6 g (8 mmol) of pyridine, 108 g ofN-methylpyrrolidone and 30 g of toluene were added in the flask. Afterstirring the mixture at 200 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 2 hours. While removing thetoluene-water azeotrope (14 ml) accumulated in the trap, the reactioncompleted.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 32,300; Weight Average Molecular Weight(Mw): 83,100; Z Average Molecular Weight (Mz): 196,000; Mw/Mn=2.58. Thispolyimide was poured into methanol to convert it to powders which weresubjected to thermal analysis. The thermal decomposition temperature ofthe polyimide was 549° C.

EXAMPLE 27

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 15 g (polyimidecontent: 3 g) of the polyimide solution obtained in Example 26 and 0.9 gof 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester, andfiltering the mixture through a filter having 3 μm diameter of pores.

(2) Formation of Images

The above-described photosensitive composition was spin-coated on 5 cmdiameter of a surface-treated copper foil (commercial product of NipponDenkai, 18 μm thickness). Thereafter, the coated layer was dried at 90°C. for 10 minutes in an infrared oven. The thickness of thisphotosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

The photosensitive layer was irradiated with an energy of 300 mJ andthen developed under the following conditions. The developer was amixture of 40 g of N-methylpyrrolidone, 25 g of aminoethanol, 25 g ofmethanol and 10 g of water. The coating layer after the irradiation wasdipped in this solution for 3 minutes, washed with deionized water,dried with an infrared lamp, and the resolution was observed. Thethickness of this polyimide layer after drying at 90° C. for 30 minuteswas about 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 20 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 15 μm was confirmed.

EXAMPLE 28

The starting mixture having the same composition as in Example 26 wasstirred at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. (bath temperature) andstirred at 180 rpm for 2.4 hours. While removing the toluene-waterazeotrope (14 ml) accumulated in the trap, the reaction completed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 46,800; Weight Average Molecular Weight(Mw): 214,000; Z Average Molecular Weight (Mz): 738,000; Mw/Mn=4.57,Mz/Mn=15.74.

The obtained composition was irradiated with light and then developed inthe same manner as in Example 26. After irradiation with light of 500mJ, the photosensitive layer was dipped in the same solution for 12minutes and washed with water. As for the line-and-space pattern,formation of sharp images of lines having a width of 15 μm wasconfirmed.

EXAMPLE 29

(1) Preparation of 9,9-bis(3-methyl-4-aminophenyl)fluorene

In the same apparatus as used in Example 24, 10 g (55.5 mmol) offluorenone, 20kg (186 mmol) of o-tolidine, 3 g (15.8 mmol) ofp-toluenesulfonic acid monohydrate, 100 g of sulfolane and 20 g oftoluene were added and the mixture was allowed to react at 180° C. for 2hours. To the reaction product, 400 mL of 10% aqueous potassiumhydroxide solution and 200 mL of water were added, and precipitates wereformed. The precipitates were recovered by decantation and washed withhot water 4 times. The resultant was then further washed twice with hotwater and then dried under reduced pressure.

(2) Preparation of Polyimide

In the same apparatus as used in Example 24, 7.53 g (20 mmol, MolecularWeight: 376.5) of the compound described above, 12.89 g (40 mmol) ofBTDA, 8.65 g (20 mmol) of m-BAPS, 0.4 g (4 mmol) of γ-valerolactone, 0.6g (8 mmol) of pyridine, 111 g of N-methylpyrrolidone and 30 g of toluenewere added, and the mixture was allowed to react at 180° C. at 180 rpmfor 3.7 hours as in Example 24.

(3) Preparation of Photosensitive Composition and Formation of Images

15 g of this reaction solution and 15 g of the reaction solution ofExample 26 were mixed, and 1.8 g of naphthoquinone diazide sulfonicacid-o-cresol ester was added thereto, followed by making the mixture toa uniform solution. By the operations similar to those in Example 25,after irradiation with light of 100 mJ, and after development for 30seconds, good images were obtained with high resolution.

EXAMPLE 30

The procedure was run the same way as Example 24.

25.7 g (80 mmol) of BTDA, 13.94 g (40 mmol) of FDA, 0.8 g (8 mmol) ofγ-valerolactone, 1.2 g (16 mmol) of pyridine, 113 g ofN-methylpyrrolidone and 30 g of toluene were added, and the mixture wasallowed to react at 180° C. at 180 rpm for 1 hour as in Example 24.

After cooling the mixture at room temperature, 16.42 g (40 mm of2,2-bis{4-(4-aminophenoxy)phenyl}propane, 100 g of N-methylpyrrolidoneand 20 g of toluene were added and the resulting mixture was allowed toreact at room temperature for 1 hour, and then heated at 180° C. at 180rpm for 1.5 hours. After the reaction, 30 g of N-methylpyrrolidone wasadded to obtain a polyimide solution having a concentration of 18%, withwhich a strong film formed by placing an aliquot of this solution on aglass plate and drying the solution at 130° C.

The molecular weights based on polystyrene measured as in Example 1were: Number Average Molecular Weight (Mn): 26,300; Weight AverageMolecular Weight (Mw): 131,700; Z Average Molecular Weight (Mz) 445,200;Mw/Mn=5.00; Mz/Mn=15.91. The thermal decomposition temperature of thepolyimide was 559° C.

In 20 g of the reaction solution, 2.8 g of naphthoquinone diazidesulfonic acid-o-cresol ester was added and the mixture was made to auniform solution. As in Example 25, the photosensitive layer wassubjected to irradiation with light of 300 mJ, heated at 170° C. for 5seconds, dipped in the developer for 2.5 minutes, washed with water anddried with infrared light. The resolution was determined using anegative-type mask and a positive-type mask. As a result, sharp circularholes with a diameter of 10 μm and sharp line images with a width of 10μm were obtained with a sensitive resolution as posi-typed good images.

EXAMPLE 31

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap. While heatingthe flask under nitrogen gas flow and under stirring, 32.22 g (100 mmol)of BTDA, 5.45 g (50 mmol) of 2,6-diaminopyridine (commercial product ofAldrich), 21.625 g (50 mmol) of m-BAPS, 1.0 g (10 mmol) ofγ-valerolactone, 1.6 g (20 mmol) of pyridine, 223 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for3.5 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 10,500; Weight Average Molecular Weight(Mw): 15,800; Z Average Molecular Weight (Mz):22,600; Mw/Mn=1.51;Mz/Mn=2.15.

EXAMPLE 32

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 15 g (polyimidecontent: 3 g) of the polyimide solution obtained in Example 31 and 0.9 gof 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester, andfiltering the mixture through a filter having 3 μm diameter of pores.

(2) Formation of Images

The above-described photosensitive composition was spin-coated on 5 cmdiameter of surface-treated copper foil (commercial product of NipponDenkai, 18 μm thickness). Thereafter, the coated layer was dried at 90°C. for 10 minutes in an infrared oven. The thickness of thisphotosensitive layer was about 10 μm.

On this photosensitive lawyer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

The photosensitive layer was irradiated with an energy of 300 mJ andthen developed under the following conditions. The developer was amixture of 40 g of N-methylpyrrolidone, 10 g of aminoethanol, 25 g ofmethanol and 25 g of water. The coating layer after the irradiation wasdipped in this solution for 1 minute and 15 seconds, washed withdeionized water, dried with an infrared lamp, and the resolution wasobserved. The thickness of this polyimide layer after drying at 90° C.for 30 minutes was about 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 33

The procedure was run the same way as Example 24.

While heating the flask under nitrogen gas flow and under stirring,29.422 g (100 mmol) of BPDA, 5.45 g (50 mmol) of 2,6-diaminopyridine(commercial product of Aldrich), 29.975 g (50 mmol) ofbis{4-(3-aminophenoxy)phenyl}hexafluoropropane (commercial product ofWakayama Seika Co., Ltd.), 1.0 g (10 mmol) of γ-valerolactone, 1.6 g (20mmol) of pyridine, 229 g of N-methylpyrrolidone and 30 g of toluene wereadded in the flask. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. and stirred at 180 rpm for 2.0 hours. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 9,300; Weight Average Molecular Weight(Mw): 14,600; Z Average Molecular Weight (Mz): 21,300; Mw/Mn=1.55;Mz/Mn=2.26.

EXAMPLE 34

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 15 g (polyimidecontent: 3 g) of the polyimide solution obtained in Example 33 and 0.9 gof 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester, andfiltering the mixture through a filter having 3 μm diameter of pores.

(2) Formation of Images

Photosensitive composition layer was prepared by the method described inExample 32(2).

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively), for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

The photosensitive layer was irradiated with an energy of 200 mJ andthen developed under the following conditions. The developer was amixture of 10 g of methanol, 20 g of 15% tetramethylammonium hydroxidesolution and 40 g of water. The coating layer after the irradiation wasdipped in this solution for 5 minutes, washed with deionized water,dried with an infrared lamp, and the resolution was observed. Thethickness of this polyimide layer after drying at 90° C. for 30 minuteswas about 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 35

The procedure was run the same way as Example 31.

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask,the condenser comprising a trapand a cooling tube having balls and mounted on the trap. While heatingthe flask under nitrogen gas flow and under stirring, 19.33 g (60 mmol)of BTDA, 3.66g (30 mmol) of 2,4-diaminotoluene, 1.0 g (10 mmol) ofγ-valerolactone, 1.6 g (20 mmol) of pyridine, 100 g ofN-methylpyrrolidone and 20 g of toluene were placed in the flask. Afterstirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. and stirredat 180 rpm for 1 hour. In the reaction, toluene-water azeotrope wasremoved.

Thereafter, 8.827 g (30 mmol) of 3,4,3′,4′-biphenyltetracarboxylicdianhydride, 3.274 g (30 mmol) of 2,6-diaminopyridine, 12.315 g (30mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}propane (Wakayama Seika Co.,Ltd.), 77 g of N-methylpyrrolidone and 10 g of toluene were added. Afterstirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated to 180° C. and stirredat 180 rpm for 1 hour. In the reaction, toluene-water azeotrope wasremoved. This second step reaction was carried out for 2 hours and 10minutes.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 12,300; Weight Average Molecular Weight(Mw): 20,000; Z Average Molecular. Weight (Mz): 29,900; Mw/Mn=1.62;Mz/Mn=2.42.

EXAMPLE 36

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 15 g (polyimidecontent: 3 g) of the polyimide solution obtained in Example 35 and 0.9 gof 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester, andfiltering the mixture through a filter having 3 μm diameter of pores.

(2) Formation of Images

Photosensitive composition layer was prepared by the method described inExample 32(2).

On this photosensitive coating membrane, a test pattern (through holesand line-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

The photosensitive layer was irradiated with an energy of 100 mJ andthen developed with the developer as used in Example 32. The coatinglayer was dipped in the solution for 1 minute, washed with deionizedwater, dried with an infrared lamp, and the resolution was observed. Thethickness of this polyimide layer after drying at 90° C. for 30 minuteswas 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 37

Two-step reaction was carried out in a basically similar manner toExample 35.

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap. While heatingthe flask under nitrogen gas flow and under stirring, 9.93 g (40 mmol)of bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride(commercial product of Aldrich), 4.00 g (20 mmol) of3,4′-diaminodiphenyl ether, 0.6 g (10 mmol) of γ-valerolactone, 1.0 g(12 mmol) of pyridine, 76 g of N-methylpyrrolidone and 30 g of toluenewere added in the flask. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. and stirred at 180 rpm for 1 hour. In the reaction,toluene-water azeotrope was removed.

Thereafter, 6.44 g (20 mmol) of BTDA, 2.18 g (20 mmol) of2,6-diaminopyridine, 8.65 g (20 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone, 40 g of N-methylpyrrolidone and 10g of toluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. and stirred at 180 rpm for 1 hour. In the reaction,toluene-water azeotrope was removed. This second step reaction wascarried out for 3 hours.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 10,300; Weight Average Molecular Weight(Mw): 14,000; Z Average Molecular Weight (Mz): 18,600; Mw/Mn=1.36;Mz/Mn=1.81

EXAMPLE 38

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 15 g (polyimidecontent: 3 g) of the polyimide solution obtained in Example 37 and 0.9 gof 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester, andfiltering the mixture through a filter having 3 μm diameter of pores.

(2) Formation of Images

Photosensitive composition layer was prepared by the method described inExample 32(2).

On this photosensitive coating membrane, a test pattern (through holesand line-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

The photosensitive layer was irradiated with an energy of 300 mJ andthen developed with the developer having the following composition. Thatis, the developer was a mixture of 3 g of potassium hydroxide and 100 gof water. The coating layer was dipped in the solution for 3 minutes,washed with deionized water, dried with an infrared lamp, and theresolution was observed. The thickness of this polyimide membrane afterdrying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 39

A stainless steel anchor agitator and reflux condenser were attached toa 1-liter three-necked separable flask, the condenser comprising a trapand a cooling tube having balls and mounted on the trap 19.33 g (60 mol)of BTDA, 5.91 g (30 mmol) of 2,4-diaminophenol dichloride (commercialproduct of Tokyo Chemical Industry Co., Ltd.), 2.98 g (30 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone (Wakayama Seika Co., Ltd.), 1.0 g(10mmol) of γ-valerolactone, 10 g (100 mmol) of N-methylmorpholine, 144g of N-methylpyrrolidone and 40 g of toluene were added.

After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 0.5 hours. While removing thetoluene-water azeotrope accumulated in the trap, the reaction completed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 42,500; Weight Average Molecular Weight(Mw): 66,000; Z Average Molecular Weight (Mz): 1,007,500; Mw/Mn=3.91;Mz/Mn=11.96. This polyimide was poured into methanol and the resultantwas filtered, followed by drying in an infrared oven at 300° C. for 30minutes to convert it to powders.

EXAMPLE 40

The procedure was run the same way as Example 39.

26.66 g (60 mmol)of 6FDA, 5.91 g (30 μmmol) of 2,4-diaminophenoldichloride (commercial product of Tokyo Chemical Industry Co., Ltd.),15.56 g (30 mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane(commercial product of Wakayama Seika Co., Ltd.), 1.0 g (10 mmol) ofγ-valerolactone, 10 g (100 mmol) of N-methylmorpholine, 184 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 70minutes 77 g of N-methylpyrrolidone was added. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 111,500; Weight Average Molecular Weight(Mw): 303,600; Z Average Molecular Weight (Mz): 682,400; Mw/Mn=2.72;Mz/Mn=6.12. An aliquot of this polyimide was poured into methanol toconvert it to powders.

EXAMPLE 41

The procedure was run the same way as Example 39.

17.65 g (60 mol) of 3,4,3′,4′-biphenyltetracarboxylic dianhydride, 5.91g (30 mmol) of 2,4-diaminophenol dichloride, 12.32 g (30 mmol) of2,2-bis{4-(4-aminophenoxy)phenyl}propane (Wakayama Seika Co., Ltd.), 1.0g (10 mmol) of γ-valerolactone, 10 g (100 mmol) of N-methylmorpholine;135g of N-methylpyrrolidone and 40 g of toluene were added. Afterstirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 1 hour. While removing thetoluene-water azeotrope accumulated in the trap, the reaction completed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 31,700; Weight Average Molecular Weight(Mw): 57,200; Z Average Molecular Weight (Mz): 89,500; Mw/Mn=1.81;Mz/Mn=2.82. This polyimide was poured into methanol and the resultantwas filtered, followed by drying in an infrared oven at 200° C. for 30minutes to convert it to powders.

EXAMPLE 42

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Tables 9 and 10 below and filtering the mixtures through a filterhaving 3 μm diameter of pores.

TABLE 9 Composition Components XV XVI XVII Polyimide Solution Example 39Example 40 Example 41 Weight 15 g 20 g 15 g (Polyimide Content)  3 g  3g  3 g 1,2-naphthoquinone-2- 0.9 g  0.9 g  0.9 g  diazide-5-sulfonicacid-o- cresol ester

TABLE 10 Composition Components XVIII XIX XX Polyimide Powder Example 39Example 40 Example 41 Polyimide Weight 3.0 g 3.0 g 3.0 g1,2-naphthoquinone-2- 0.9 g 0.9 g 0.9 g diazide-5-sulfonic acid-o-cresol ester N-methylpyrrolidone 12 g  12 g  12 g 

(2) Formation of Images

Each of the above-described 6 photosensitive layers was spin-coated on 5cm 5 diameter of a surface-treated copper foil (commercial product ofNippon Denkai, 18 μm thickness). Thereafter, the coated composition wasdried at 90° C. for 10 minutes in an infrared hot air dryer. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive coating layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

Each of the compositions XV-XX was irradiated with UV light with anappropriate dose shown in Table 11 below, and then developed under theconditions shown in Table 11. The coating layer after irradiation withUV light was dipped in this solution under the conditions shown in Table11, washed with deionized water, dried with an infrared lamp, and theresolution was observed. The thickness of this polyimide layer afterdrying at 90° C. for 30 minutes was 9 μm.

TABLE 11 Composition XV XVI XVII XVIII XIX XX Dose of Irradiated 500 300300 500 500 300 UV Light (mJ) Dipping Time 5 10 230 197 240 600 (second)Composition of 1 1 2 1 1 2 Dipping Solution

(Composition 1: 40 g of N-methylpyrrolidone, 10 g of aminoethanol, 25 gof methanol and 25 g of water)

(Composition 2: 3 g of potassium hydroxide and 100 g of water)

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 43

The procedure was run the same way as Example 39.

11.77 g (40 mol) of 3,4,3′,4′-biphenyltetracarboxylic dianhydride, 4.29g (20 mmol) of 3,3′-dihydroxy-4,4′-diaminobiphenyl (Wakayama Seika Co.,Ltd.), 5.85 g (20 mmol) of 1,3-bis(4-aminophenoxy)benzene (WakayamaSeika Co., Ltd.), 0.8 g (8 mmol) of γ-valerolactone, 1.6 g (20 mmol) ofpyridine, 82 g of N-methylpyrrolidone and 40 g of toluene were added.After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 1 hour. While removing thetoluene-water azeotrope accumulated in the trap, the reaction completed.After the reaction, 34 g of N-methylpyrrolidone was added.

The polymer concentration thus obtained was 18% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 31,800; Weight Average Molecular Weight(Mw): 59,600; Z Average Molecular Weight (Mz): 102,300; Mw/Mn=1.87;Mz/Mn=3.22. This polyimide solution was poured into methanol and theresultant was filtered, followed by drying in an infrared oven at 200°C. for 30 minutes to convert it to powders which were subjected tothermal analysis. The thermal decomposition temperature was 559° C.

EXAMPLE 44

The procedure was run the same way as Example 39.

12.87 g (40 mol) of 3,4,3′,4′-biphenyltetracarboxylic dianhydride, 4.29g (20 mmol) of 3,3′-dihydroxy-4,4′-diaminobiphenyl (Wakayama Seika Co.,Ltd.), 8.65 g (20 mmol) of bis-{4-(3-aminophenoxy)phenyl}sulfone(Wakayama Seika Co., Ltd.), 0.8 g (8 mmol) of γ-valerolactone, 1.2 g (16mmol) of pyridine, 98 g of N-methylpyrrolidone and 40 g of toluene wereadded. After stirring the mixture at 180 rpm at room temperature undernitrogen atmosphere for 30 minutes, the mixture was heated at 180° C.(bath temperature) and stirred at 180 rpm for 1.5 hours. While removingthe toluene-water azeotrope accumulated in the trap, the reactioncompleted.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 19,000; Weight Average Molecular Weight(Mw): 35,800; Z Average Molecular Weight (Mz): 60,300; Mw/Mn=1.86;Mz/Mn=3.14. An aliquot of this polyimide was poured into methanol andthe resultant was filtered, followed by drying in an infrared oven at200° C. for 30 minutes to convert it to powders which were subjected tothermal analysis. The thermal decomposition temperature was 552° C.

EXAMPLE 45

The procedure was run the same way as Example 39.

17.77 g (40 mol) of 6FDA, 4.29 g (20 mmol) of3,3′-dihydroxy-4,4′-diaminobiphenyl (Wakayama Seika Co., Ltd.), 8.65 g(20 mmol) of bis-{4-(3-aminophenoxy)phenyl}sulfone (Wakayama Seika Co.,Ltd.), 0.8 g (8 mmol) of γ-valerolactone, 1.2 g (16 mmol) of pyridine,117 g of N-methylpyrrolidone and 40 g of toluene were added. Afterstirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 3.7 hours. While removing thetoluene-water azeotrope accumulated in the trap, the reaction completed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 111,600; Weight Average Molecular Weight(Mw): 196,000; Z Average Molecular Weight (Mz): 311,700; Mw/Mn=1.76;Mz/Mn=2.79. This polyimide was poured into methanol and the resultantwas filtered, followed by drying in an infrared oven at 200° C. for 30minutes to convert it to powders which were subjected to thermalanalysis. The thermal decomposition temperature was 552° C.

EXAMPLE 46

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 12 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 12 Composition Components XXI XXII XXIII Polyimide SolutionExample 43 Example 44 Example 45 Weight  15 g  15 g  15 g (PolyimideContent) 2.7 g   3 g   3 g 1,2-naphthoquinone-2- diazide-5-sulfonicacid-o- 0.9 g 0.9 g 0.9 g cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (XXI, XXII andXXIII) was spin-coated on 5 cm diameter of surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness) by spin coatingmethod. Thereafter, the coated layer was dried at 90° C. for 10 minutesin an infrared oven. The thickness of this photosensitive layer wasabout 10 μm.

On this photosensitive coating layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

Each of the compositions XXI, XXII and XXIII was irradiated with UVlight with an appropriate dose shown in Table 13 below, and thendeveloped under the conditions shown in Table 13. The coating layerafter irradiation with UV light was dipped in this solution under theconditions shown in Table 13, washed with deionized water, dried with aninfrared lamp, and the resolution was observed. The thickness of thispolyimide layer after drying at 90° C. for 30 minutes was 9 μm.

TABLE 13 Composition XXI XXII XXIII Dose of Irradiated 200 300 300 UVLight (mJ) Dipping Time  60  5  60 (second) Composition of  3  3  3Dipping Solution

(Composition 3: 20 g of aminoethanol, 10 g of glycerin and 50 g ofwater)

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

The polyimide coating layer was then heated in infrared oven at 260° C.for 30 minutes, and the adhesion between the polyimide membrane and thecopper foil was evaluated by cross cut test (1 mm×1 mm interval crosstest). As a result, 100/100 lattices remained adhered, so that theadhesion between the polyimide layer and the copper foil was good.

EXAMPLE 47

The procedure was run the same way as Example 39.

12.89 g (40 mmol) of BTDA, 8.65 g (20 mmol) ofbis-{4-(3-aminophenoxy)phenyl}sulfone, 0.4 g (4 mmol) ofγ-valerolactone, 0.64 g (8 mmol) of pyridine, 77 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. (bath temperature) andstirred at 180 rpm for 1 hour. While removing the toluene-waterazeotrope accumulated in the trap, the reaction completed.

2.16 g (10 mmol) of 3,3′-dihydroxy-4,4′-diaminobiphenyl, 2.00 g (10mmol) of 3,4′-diaminodiphenyl ether, 20 g of N-methylpyrrolidone and 10g of toluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. (bath temperature) and stirred at 180 rpm for 1.0hour. While removing the toluene-water azeotrope accumulated in thetrap, the reaction completed. After the reaction, 41 g ofN-methylpyrrolidone was added.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 32,300; Weight Average Molecular Weight(Mw): 140,200; Z Average Molecular Weight (Mz): 442,000; Mw/Mn=4.34;Mz/Mn=13.68. This polyimide solution was poured into methanol and theresultant was filtered, followed by drying in an infrared oven at 200°C. for 30 minutes to convert it to powders which were subjected tothermal analysis. The thermal decomposition temperature was 569° C.

EXAMPLE 48

The procedure was run the same way as Example 39.

9.93 g (40 mmol) of bicyclo(2,2,2)-oct-2,3,5,6-tetracarboxylicdianhydride (commercial product of Aldrich), 5.85 g (20 mmol) of1,3-bis-(3-aminophenoxy)benzene (commercial product of Mitsui ToatsuChemicals, Inc.), 0.4 g (4 mmol) of γ-valerolactone, 0.64 g (8 mmol) ofpyridine, 55 g of N-methylpyrrolidone and 30 g of toluene were added.After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 1.0 hour. In the reaction,toluene-water azeotrope accumulated in the trap was removed. Aftercooling the mixture, 4.32 g (20 mmol) of3,3′-dihydroxy-4,4′-diaminobiphenyl, 20 g of N-methylpyrrolidone and 10g of toluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. (bath temperature) and stirred at 180 rpm for 1.45hours. The toluene-water azeotrope accumulated in the trap was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 54,300; Weight Average Molecular Weight(Mw): 88,400; Z Average Molecular Weight (Mz): 130,400; Mw/Mn=2.16;Mz/Mn=2.40. This polyimide was poured into methanol and the resultantwas filtered, followed by drying in an infrared oven at 200° C. for 30minutes to convert it to powders which were subjected to thermalanalysis. The thermal decomposition temperature was 457° C.

EXAMPLE 49

The procedure was run the same way as Example 47.

Operations basically similar to those in Example 47 were carried out.

29.42 g (100 mmol) of biphenyltetracarboxylic dianhydride, 41.6 g (50mmol) of diaminosilane (commercial product of Shin-etsu Chemical Co.,Ltd., amine equivalent: 416), 1.5 g (15 mmol) of γ-valerolactone, 2.4 g(30 mmol) of pyridine, 200 g of N-methylpyrrolidone and 100 g of toluenewere added.

After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 1 hour. While removing thetoluene-water azeotrope accumulated in the trap, the reaction completed.

In this mixture, 16.11 g (50 mmol) of BTDA, 10.72 g (50 mmol) of3,3′-dihydroxy-4,4′-diaminobiphenyl, 10.01 g (50 mol) of3,4′-diaminodiphenyl ether, 210 g of N-methylpyrrolidone and 20 g oftoluene were added. After 'stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. (bath temperature) and stirred at 180 rpm for 3.0hours. While removing the toluene-water azeotrope accumulated in thetrap, the reaction completed.

The polymer concentration thus obtained was 10% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 33,000; Weight Average Molecular Weight(Mw): 66,300; Z Average Molecular Weight (Mz): 116,700; Mw/Mn=2.0;Mz/Mn=3.53.

EXAMPLE 50

The operations similar to those in Example 46 were carried out for thepolyimides obtained in Examples 47, 48 and 49.

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 14 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 14 Composition Components XXIV XXV XXVI Polyimide Solution Example47 Example 48 Example 49 Weight  20 g  15 g  30 g (Polyimide Content)  3 g   3 g   3 g 1,2-naphthoquinone-2- diazide-5-sulfonic acid-o- 0.9 g0.9 g 0.9 g cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (XXIV, XXV andXXVI) was spin-coated on 5 cm diameter of surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

Each of the compositions XXIV, XXV and XXVI was irradiated with UV lightwith an appropriate dose shown in Table 15 below, and then developedunder the conditions shown in Table 15. The coating layer afterirradiation with UV light was dipped in this solution under theconditions shown in Table 15, washed with deionized water, dried with aninfrared lamp, and the resolution was observed. The thickness of thispolyimid layer after drying at 90° C. for 30 minutes was 9 μm.

TABLE 15 Composition XXIV XXV XXVI Dose of Irradiated 300 300 300 UVLight (mJ) Dipping Time 170  30  4 (second) Composition of  1  1  3Dipping Solution

(Composition 1: 40 g of N-methylpyrrolidone, 10 g of aminoethanol, 25 gof methanol and 25 g of water)

(Composition 3: 20 g of aminoethanol, 10 g of glycerin and 50 g ofwater).

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 51

The procedure was run the same way as Example 39.

38.67 g (120 mmol) of BTDA, 11.00 g (90 mmol) of 2,4-diaminotoluene,7.33 g (30 mmol) of 3,3′-dimethoxy-4,4′-diaminobiphenyl (commercialproduct of Wakayama Seika Co., Ltd.), 1.2 g (12 mmol) ofγ-valerolactone, 1.9 g (24 mmol) of pyridine, 211 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. (bath temperature) andstirred at 180 rpm for 3.0 hours. In the reaction, toluene-waterazeotrope accumulated in the trap was removed. Toluene-water azeotropeaccumulated in the trap was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 20,360; Weight Average Molecular Weight(Mw): 40,200; Z Average Molecular Weight (Mz): 72,200; Mw/Mn=1.98;Mz/Mn=3.55.

EXAMPLE 52

26.66 g (60 mmol) of 6FDA, 10.37 g (20 mmol) ofbis-{4-(3-aminophenoxy)phenyl}hexafluoropropane (commercial product ofWakayama Seika Co., Ltd.), 4.89 g (20 mmol) of3,3′-dimethoxy-4,4′-diaminobiphenyl, 4.25 g (20 mmol) of3,3′-dimethyl-4,4′-diaminobiphenyl, 0.6 g (6 mmol) of γ-valerolactone,1.0 g (12 mmol) of pyridine, 176 g of N-methylpyrrolidone and 40 g oftoluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. (bath temperature) and stirred at 180 rpm for 1.75hours. While removing the toluene-water azeotrope accumulated in thetrap, the reaction completed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 23,600; Weight Average Molecular Weight(Mw): 34,400; Z Average Molecular Weight (Mz): 49,600; Mw/Mn=1.45;Mz/Mn=2.06.

EXAMPLE 53

The operations similar to those in EXAMPLE 42 were carried out for thepolyimides obtained in Examples 51 and 52;

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 16 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 16 Composition Components XXVII XXVIII Polyimide Solution Example51 Example 52 Weight  15 g  15 g (Polyimide Content)   3 g   3 g1,2-naphthoquinone-2- diazide-5-sulfonic acid-o- 0.9 g 0.9 g cresolester

(2) Formation of Images

Each of the above-described photosensitive compositions (XXVII andXXVIII) was spin-coated on 5 cm diameter of a surface-treated copperfoil (commercial product of Nippon Denkai, 18 μm thickness). Thereafter,the coated layer was dried at 90° C. for 10 minutes in an infrared oven.The thickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho).

Each of the compositions XXVII and XXVIII was irradiated with UV lightwith an appropriate dose shown in Table 17 below, and then developedunder the conditions shown in Table 17. The coating layer afterirradiation with UV light was dipped in this solution under theconditions shown in Table 17, washed with deionized water, dried with aninfrared lamp, and the resolution was observed. The thickness of thispolyimide layer after drying at 90° C. for 30 minutes was about 9 μm.

TABLE 17 Composition XXVII XXVIII Dose of Irradiated 300 220 UV Light(mJ) Dipping Time 210 150 (second) Composition of  3  3 Dipping Solution

(Composition 3: 20 g of aminoethanol, 10 g of glycerin and 50 g ofwater)

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 54

A condenser tube with a ball, having a water separation trap, wasmounted on a one-liter separable three-necked flask equipped with ananchor-shaped stirrer made of stainless steel. In the flask, 26.66 g (60mmol) of 6FDA, 5.48 g (20 mmol) of 3,3′-dinitro-4,4′-diaminobiphenyl(commercial product of Tokyo Chemical Industry Co., Ltd.), 8.49 g (40mmol) of 3,3′-dimethyl-4,4′-diaminobiphenyl (Wakayama Seika Co., Ltd.),0.8 g (8 mmol) of γ-valerolactone, 1.6 g (16 mmol) ofN-methylmorpholine, 154 g of N-methylpyrrolidone and 40 g of toluenewere added. After stirring the mixture at 180 rpm at room temperatureunder nitrogen atmosphere for 30 minutes, the mixture was heated at 180°C. and stirred at 180 rpm for 7.50 hours. In the reaction, toluene-waterazeotrope accumulated in the trap was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 7100; Weight Average Molecular Weight(Mw): 10,000; Z Average Molecular Weight (Mz): 14,000; Mw/Mn=1.41;Mz/Mn=1.97.

EXAMPLE 55

The procedure was run the same way as Example 54.

26.66 g (60 mmol) of 6FDA, 5.48 g (20 mmol) of3,3-dinitro-4,4-diaminobiphenyl, 4.25 g (20 mmol) of3,3-dimethyl-4,4-diaminobiphenyl, 10.37 g (20 mmol) of2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane, 0.8 g (8 mmol) ofγ-valerolactone, 1.2 g (16 mmol) of pyridine, 178 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 4hours. In the reaction, toluene-water azeotrope accumulated in the trapwas removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 7400; Weight Average Molecular Weight(Mw): 9600; Z Average Molecular Weight (Mz): 12,400; Mw/Mn=1.29;Mz/Mn=1.66.

EXAMPLE 56

The procedure was run the same way as Example 54.

19.33 g (60 mol) of.BTDA, 5.48 g (20 mmol) of3,3′-dinitro-4,4′-diaminobiphenyl, 2.44 g (20 mmol) of2,4-diaminotoluene (commercial product of Mitsui Toatsu Chemicals,Inc.), 8.65 g (20 mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 0.8 g(8 mmol) of γ-valerolactone, 1.2 g (16 mmol) of pyridine, 123 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for4.25 hours; In the reaction, toluene-water azeotrope accumulated in thetrap was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 5300; Weight Average Molecular Weight(Mw): 7200; Z.Average Molecular Weight (Mz):9600; Mw/Mn=1.37;Mz/Mn=1.81.

EXAMPLE 57

The procedure was run the same way as Example 54.

17.77 g (40 mol) of 6FDA, 5.48 g (20 mmol) of3,3′-dinitro-4,4′-diaminobiphenyl, 10.37 g (20 mmol) of2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane, 0.4 g (4 mmol) ofγ-valerolactone, 0.8 g (8 mmol) of N-methylmorpholine, 129 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for5.5 hours. In the reaction, toluene-water azeotrope accumulated in thetrap was removed. The polymer concentration thus obtained was 20% byweight. The molecular weights based on polystyrene measured by highperformance liquid chromatography (commercial product of TosohCorporation) were: Number Average Molecular Weight (Mn): 4900; WeightAverage Molecular Weight (Mw): 6700; Z Average Molecular Weight(Mz):9200; Mw/Mn=1.37; Mz/Mn=1.89.

EXAMPLE 58

The procedure was run the same way as Example 54.

16.11 g (50 mol) of BTDA, 6.86 g (25 mmol) of3,3′-dinitro-4,4′-diaminobiphenyl, 10.81 g (25 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone, 0.5 g (5 mmol) of γ-valerolactone,1.0 g (10 mmol) of N-methylmorpholine, 128 g of N-methylpyrrolidone and40 g of toluene were added. After stirring the mixture at 180 rpm atroom temperature under nitrogen atmosphere for 30 minutes, the mixturewas heated at 180° C. and stirred at 180 rpm for 5.75 hours. In thereaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 4300; Weight Average Molecular Weight(Mw): 6100; Z Average Molecular Weight (Mz): 8500; Mw/Mn=1.40;Mz/Mn=1.95.

EXAMPLE 59

(1) Preparation of Photosensitive Compositions

Photosensitive compositions (XXIX-XXXIII) were prepared by mixing thepolyimide solutions obtained in Examples 54 to 58 described above withother components shown in Table 18below and filtering the mixturesthrough a filter having 3 μm diameter of pores.

TABLE 18 Composition Components XXIX XXX XXXI XXXII XXXIII PolyimideSolution Ex. 54 Ex. 55 Ex. 56 Ex. 57 Ex. 58 Weight  15 g  15 g  15 g  15g  15 g (Polyimide Content)   3 g   3 g   3 g   3 g   3 g1,2-naphthoquinone-2- diazide-5-sulfonic acid- 0.9 g 0.9 g 0.9 g 0.9 g0.9 g o-cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (XXIX-XXXIII)was spin-coated on 5 cm diameter of surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained shown in Table 19 below using 2 kW extra-highpressure mercury lamp apparatus (JP-2000G, commercial product of OakSeisakusho).

Each of the compositions (XXIX-XXXIII) was irradiated with UV light withthe dose shown in Table 19 below, and then developed under theconditions shown in Table 19.

TABLE 19 Composition XXIX XXX XXXI XXXII XXXIII Dose of Irradiated UV500 600 500 300 500 Light (mJ) Dipping Time (minute)  3  5  3 (second) 54  37 Composition of  1  1  1  2  2 Developer

Composition of Developer 1 was made of 30 g of potassium hydroxide and100 g of water, and Composition of Developer 2 was made of 40 g ofN-methylpyrrolidone, 10 g of aminoethanol, 10 g of methanol and 25 g ofwater. Each of the coating layer after irradiation with UV light wasdipped in this solution for the time period mentioned above, washed withdeionized water, dried with an infrared lamp, and the resolution wasobserved. The thickness of this polyimide layer after drying at 90° C.for 30 minutes was about 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 60

The procedure was run the same way as Example 54.

22.21 g (50 mol) of 6FDA, 3.83 g (25 mmol) of2-nitro-1,4-diaminobenzene, 12.96 g (25 mmol) of2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane, 0.5 g (5 mmol) ofγ-valerolactone, 1.0 g (10 mmol) of N-methylmorpholine, 149 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 4hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 4800; Weight Average Molecular Weight(Mw): 6400; Z Average Molecular Weight (Mz): 9600; Mw/Mn=1.43;Mz/Mn=2.00.

EXAMPLE 61

The procedure was run the same way as Example 54.

14.71 g (50 mol) of 3,4,3′,4′-biphenyltetracarboxylic dianhydride, 3.83g (25 mmol) of 2-nitro-1,4-diaminobenzene, 5.01 g (25 mmol) of3,4′-diaminodiphenyl ether, 0.5 g (5 mmol) of γ-valerolactone; 1.0 g (10mmol) of N-methylmorpholine, 87 g of N-methylpyrrolidone and 40 g oftoluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. and stirred at 180 rpm for 4 hours. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 2900; Weight Average Molecular Weight(Mw): 3700; Z Average Molecular Weight (Mz): 4900; Mw/Mn=1.25;Mz/Mn=1.69.

EXAMPLE 62

The procedure was run the same way as Example 54.

16.11 g (50 mol) of BTDA, 3.83 g (25 mmol) of2-nitro-1,4-diaminotoluene, 10.81 g (25 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone, 5.01 g (25 mmol) of3,4′-diaminodiphenyl ether, 0.5 g (5 mmol) of γ-valerolactone, 1.0 g (10mmol) of N-methylmorpholine, 116 g of N-methylpyrrolidone and 40 g oftoluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. and stirred at 180 rpm for 3 hours. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 4300; Weight Average Molecular Weight(Mw): 5800; Z Average Molecular Weight (Mz): 7700; Mw/Mn=1.34;Mz/Mn=1.78.

EXAMPLE 63

Using the polyimide solutions prepared in Examples 60 to 62,photosensitive compositions as in Example 59 were prepared, and imageswere formed with 2 kW extra-high pressure mercury lamp apparatus underthe conditions shown in Table 20.

TABLE 20 Polyimide Solution Example 60 Example 61 Example 62 Dose ofIrradiated 500 550 350 UV Light (mJ) Dipping Time 130 180  30 (second)Composition of  3  3  3 Developer

Composition of Developer 3 was made of 40 g of N-methylpyrrolidone, 10 gof aminoethanol, 25 g of methanol and, 25 g of water. Each of thecoating layer after irradiation with UV light was dipped in thissolution for the time period shown in Table 20, washed with deionizedwater, dried with an infrared lamp, and the resolution was observed. Thethickness of this polyimide layer after drying at 90° C. for 30 minuteswas 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 64

The procedure was run the same way as Example 54.

22.21 g (50 mol) of 6FDA, 5.96 g (25 mmol) of 1,5-diaminoanthraquinone(Tokyo Chemical Industry Co., Ltd.), 12.96 g (25 mmol)of2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane (25 mmol), 0.5 g (5mmol) of γ-valerolactone, 0.8 g (10 mmol) of pyridine, 157 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 7hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 4600; Weight Average Molecular Weight(Mw): 6500; Z Average Molecular Weight (Mz): 8800; Mw/Mn=1.42;Mz/Mn=1.93.

EXAMPLE 65

The procedure was run the same way as Example 54.

19.33 g (60 mol) of BTDA, 7.14 g (30 mmol) of 1,5-diaminoanthraquinone,12.98 g (30 mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 0.6 g ofγ-valerolactone, 1.0 g of pyridine, 149 g of N-methylpyrrolidone and 40g of toluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. and stirred at 180 rpm for 3 hours. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 3800; Weight Average Molecular Weight(Mw): 5500; Z Average Molecular Weight (Mz): 7500; Mw/Mn=1.43;Mz/Mn=1.94.

EXAMPLE 66

The procedure was run the same way as Example 54.

17.65 g (60 mol) of 3,4,3′,4′-biphenyltetracarboxylic dianhydride, 7.14g (30 mmol) of 1,5-diaminoanthraquinone, 12.32 g (20 mmol) of2,2-bis{4-(3-aminophenoxy)phenyl}propane, 0.6 g of γ-valerolactone; 1.0g of pyridine, 140 g of N-methylpyrrolidone and 40 g of toluene wereadded. After stirring the mixture at 180 rpm at room temperature undernitrogen atmosphere for 30 minutes, the mixture was heated at 180° C.and stirred at 180 rpm for 7 hours. In the reaction, toluene-waterazeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 3300; Weight Average Molecular Weight(Mw): 4800; Z Average Molecular Weight (Mz): 6700; Mw/Mn=143;Mz/Mn=2.01.

EXAMPLE 67

Using the polyimide solutions prepared in Examples 64 to 66,photosensitive compositions as in Example 59 were prepared, and imageswere formed with 2kW extra-high pressure mercury lamp apparatus underthe conditions shown in Table 21.

TABLE 21 Polyimide Solution Example 64 Example 65 Example 66 Dose ofIrradiated 500 300 300 UV Light (mJ) Dipping Time  34  35  88 (second)Composition of  4  4  4 Developer

Composition of Developer 4 was made of 10 g of methanol, 40 g of waterand 20 g of 15% tetramethylammonium hydroxide solution. Each of thecoating layer after irradiation with UV light was dipped in thissolution for the time period shown in Table 21, washed with deionizedwater, dried with an infrared lamp, and the resolution was observed. Thethickness of this polyimide layer after drying at 90° C. for 30 minuteswas 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 68

A condenser tube with a ball, having a water separation trap, wasmounted on a 1-liter separable three-necked flask equipped with ananchor-shaped stirrer made of stainless steel. In the flask, 26.66 g (60mmol) of 6FDA, 4.33 g (20 mmol) of 4,4′-diaminodiphenyl sulfide, 20.74 g(40 mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane(commercial product of Wakayama Seika Co., Ltd.), 0.6 g (6 mmol) ofγ-valerolactone, 1.0 g (12 mmol) of pyridine, 198 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for2.25 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 33,900; Weight Average Molecular Weight(Mw): 57,200; Z Average Molecular Weight (Mz):94,200; Mw/Mn=1.75;Mz/Mn=2.78.

EXAMPLE 69

The procedure was run the same way as Example 68.

19.33 g (60 mmol) of BTDA, 4.33 g (20 mmol) of 4,4′-diaminodiphenylsulfide, 17.3 g (40 mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone(commercial product of Wakayama Seika Co., Ltd.), 0.6 g (6 mmol) ofγ-valerolactone, 1.0 g (12 mmol) of pyridine, 155 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for2.24 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 42,200; Weight Average Molecular Weight(Mw): 126,500; Z Average Molecular Weight (Mz): 334,900; Mw/Mn=3.00;Mz/Mn=7.93.

EXAMPLE 70

The procedure was run the same way as Example 68.

17.65 g (60 mmol) of 3,4,3′,4′-benzophenone tetracarboxylic dianhydride,4.33 g (20 mmol) of 4,4′-diaminodiphenyl sulfide, 8.01 g (40 mmol) of3,4′-diaminodiphenyl ether (commercial product of Mitsui PetrochemicalCo., Ltd.), 0.6 g (6 mmol) of γ-valerolactone, 0.96 g of pyridine, 111 gof N-methylpyrrolidone and 40 g of toluene were added. After stirringthe mixture at 200 rpm at room temperature under nitrogen atmosphere for30 minutes, the mixture was heated at 180° C. and stirred at 180 rpm for2.0 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 44,000; Weight Average Molecular Weight(Mw): 136,200; Z Average Molecular Weight (Mz): 368,800; Mw/Mn=3.10;Mz/Mn=8.38.

EXAMPLE 71

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 22 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 22 Composition Components XL XLI XLII Polyimide Solution Example68 Example 69 Example 70 Weight  15 g  15 g  15 g (Polyimide Content)  3 g   3 g   3 g 1,2-naphthoquinone-2- 0.9 g 0.9 g 0.9 gdiazide-5-sulfonic acid-o- cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (XL, XLI andXLII) was spin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of each of these photosensitive membranes was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layer were irradiated at a dose ofexposure of at which images are obtained, that is with 300 mJ using 2 kWextra-high pressure mercury lamp apparatus (JP-2000G, commercial productof Oak Seisakusho). After irradiation, each coating layer was developedin the developer for 28 minutes (Composition IL), 8 minutes (CompositionILI) or 13 minutes (Composition ILII). The developer was a mixture of 40g of N-methylpyrrolidone, 10 g of aminoethanol, 25 g of methanol and 25g of water. Each of the coating layers after the irradiation was dippedin this solution for the time period mentioned above, washed withdeionized water, dried with an infrared lamp, and the resolution wasobserved. The thickness of this polyimide layer after drying at 90° C.for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 72

The procedure was run the same way as Example 68.

9.93 g (40 mol) of BCD, 12.98 g (60 mmol) of 4,4′-diaminodiphenylsulfide, 1.2 g (12 mmol) of γ-valerolactone, 1.4 g (18 mmol) ofpyridine, 150 g of N-methylpyrrolidone and 30 g of toluene were added.After stirring the mixture at 200 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 2 hours. While removing thetoluene-water azeotrope accumulated in the trap, the reaction completed.

After cooling the mixture at room temperature, 23.53 g (80 mmol) of3,4,3′,4′-benzophenone tetracarboxylic dianhydride, 17.54 g (60 mmol) of1,3-bis(4-aminophenoxy)benzene (Wakayama Seika Co., Ltd.), 89 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 170° C. (bath temperature) andstirred at 180 rpm for 4 hours. While adding 100 g ofN-methylpyrrolidone and while removing the toluene-water azeotrope (15ml) accumulated in the trap, the reaction completed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 22,700; Weight Average Molecular Weight(Mw): 40,800; Z Average Molecular Weight (Mz): 65,600; Mw/Mn=1.80;Mz/Mn=2.89.

EXAMPLE 73

The procedure was run the same way as Example 72.

19.86 g (80 mol) of BCD, 25.96 g (120 mmol) of 4,4′-diaminodiphenylsulfide, 2.4 g (24 mmol) of γ-valerolactone, 4.86 g (48 mmol) ofN-methylmorpholine, 250 g of N-methylpyrrolidone and 30 g of toluenewere added. After stirring the mixture at 200 rpm at room temperatureunder nitrogen atmosphere for 30 minutes, the mixture was heated at 180°C. (bath temperature) and stirred at 180 rpm for 1 hour. While removingthe toluene-water azeotrope accumulated in the trap, the reactioncompleted:

After cooling the mixture to room temperature, 47.08 g (160 mmol) ofBPDA, 49.26 g (120 mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 284 gof N-methylpyrrolidone and 30 g of toluene were added.

After stirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. (bathtemperature) and stirred at 180 rpm for 3.20 hours. While adding 223 gof N-methylpyrrolidone and while removing the toluene-water azeotropeaccumulated in the trap, the reaction completed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 3.9,600; Weight Average Molecular Weight(Mw): 61,500; Z Average Molecular Weight (Mz): 83,400; Mw/Mn=1.55;Mz/Mn=2.11.

EXAMPLE 74

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 23 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 23 Composition Components XLIII XLIV Polyimide Solution Example 72Example 73 Weight  20 g  20 g (Polyimide Content)   3 g   3 g1,2-naphthoquinone-2-diazide-5- 0.9 g 0.9 g sulfonic acid-o-cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (XLIII and XLIV)was spin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layers were irradiated at a dose ofexposure of at which images are obtained using 2 kW extra-high pressuremercury lamp apparatus (JP-2000G, commercial, product of OakSeisakusho). The dose of irradiated UV was 300 mJ. After irradiation,each coating layer was developed with the developer for 24 minutes(Composition XLIII) or 5 minutes (Composition XLIV). The developingsolution was a mixture of 40 g of N-methylpyrrolidone, 10 g ofaminoethanol, 25 g of methanol and 25 g of water.

Each of the coating layer after the irradiation was dipped in thissolution for the time period mentioned above, washed with deionizedwater, dried with an infrared lamp, and the resolution was observed. Thethickness of each polyimide layer after drying at 90° C. for 30 minuteswas about 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 20 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 15 μm was confirmed.

EXAMPLE 75

A condenser tube with a ball, having a water separation trap, wasmounted on a 0.5-L separable three-necked flask equipped with ananchor-shaped stirrer made of stainless steel.

In the flask, 32.22 g (100 mmol) of BTDA, 10.01 g (50 mmol) of1,4-bis(3-aminopropyl)piperazine (commercial product of Tokyo ChemicalIndustry Co., Ltd.), 21.6 g (50 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone (commercial product of WakayamaSeika Co., Ltd.), 1.0 g (10 mmol) of γ-valerolactone, 1.6 g (20 mmol) ofpyridine, 240 g of N-methylpyrrolidone and 30 g of toluene were added.After stirring the mixture at 200 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. and stirredat 180 rpm for 3 hours. In the reaction, toluene-water azeotrope wasremoved.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 6100; Weight Average Molecular Weight(Mw): 8700; Z Average Molecular Weight (Mz): 11,600; Mw/Mn=1.42;Mz/Mn=1.90.

EXAMPLE 76

The procedure was run the same way as Example 75.

23.54 g (80 mmol) of BPDA, 4.01 g (20 mmol) of1,3-bis(3-aminopropyl)piperazine, 24.63 g (60 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone, 0.8 g (8 mmol) of γ-valerolactone,1.0 g (12 mmol) of pyridine, 262 g of N-methylpyrrolidone and 40 g oftoluene were added. After stirring the mixture at 200 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. and stirred at 180 rpm for 2.3 hours. In the reaction,toluene-water azeotrope was removed.

The polymer concentration thus obtained was 15% by weight.

EXAMPLE 77

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 26 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 26 Composition Components XLVIII XLIX Polyimide Solution Example75 Example 76 Weight  15 g  20 g (Polyimide Content)   3 g   3 g1,2-naphthoquinone-2-diazide-5- 0.9 g 0.9 g sulfonic acid-o-cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (XLVIII andXLIX) was spin-coated on 5 cm diameter of a surface-treated copper foilhaving a diameter of 5 cm (commercial product of Nippon Denkai, 18 μmthickness) by spin coating method. Thereafter, the coated compositionwas dried at 90° C. for 10 minutes in an infrared oven. The thickness ofthis photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained shown in Table 27 below using 2 kW extra-highpressure mercury lamp apparatus (JP-2000G, commercial product of OakSeisakusho).

TABLE 27 Composition XLVIII XLIX Dose of Irradiated UV Light (mJ) 300500 Development Time (minute) 2.75 7.5

The developer was a mixture of 40 g of N-methylpyrrolidone, 10 g ofaminoethanol, 25 g of methanol and 25 g of water. Each of the coatinglayer after irradiation with UV light was dipped in this solution forthe time period mentioned above, washed with deionized water, dried withan infrared lamp, and the resolution was observed. The thickness of thispolyimide layer after drying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 78

The procedure was run the same way as Example 75.

13.09 g (60 mmol) of pyromellitic dianhydride, 29.46 g (30 mmol) ofdiaminosilane (commercial product of Shin-etsu Chemical Co., Ltd., amineequivalent: 416), 1.0 g (10 mmol) of γ-valerolactone, 1.6 g (20 mmol) ofpyridine, 150 g of N-methylpyrrolidone and 70 g of toluene were added.After stirring the mixture at 200 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. and stirredat 180 rpm for 1 hour. In the reaction, toluene-water azeotrope wasremoved.

After cooling the mixture at room temperature, 8.83 g (30 mmol) of3,4,3′,4′-biphenyltetracarboxylic dianhydride, 6.01 g (30 mmol) of1,3-bis(3-aminopropyl)piperazine, 12.32 g (30 mmol of2,2-bis{4-(4-aminophenoxy)phenyl}propane, 98 g of N-methylpyrrolidoneand 20 g of toluene were added. After stirring the mixture at 180 rpm atroom temperature under nitrogen atmosphere for 30 minutes, the mixturewas heated at 180° C. and stirred at 180 rpm for 4 hours. In thereaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 16,200; Weight Average Molecular Weight(Mw): 22,200; Z Average Molecular Weight (Mz): 29,200; Mw/Mn=1.37;Mz/Mn=1.80.

EXAMPLE 79

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared as in Example 78 using thepolyimide solution obtained in Example 78.

(2) Formation of Images

The photosensitive composition was spin-coated on 5 cm diameter ofsurface-treated copper foil (commercial product of Nippon Denkai, 18 μmthickness). Thereafter, the, coated layer was dried at 90° C. forminutes in an infrared oven. The thickness of this photosensitive layerwas about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained, that is, irradiated with 100 mJ of UV using 2kW extra-high pressure mercury lamp apparatus (JP-2000G, commercialproduct of Oak Seisakusho). Then development was carried out for 22seconds. The developer was a mixture of 30 g of aminoethanol, 50 g ofethanol and 15 g of water. The coating layer after irradiation with UVlight was dipped in this solution for the time period mentioned above,washed with deionized water, dried with an infrared lamp, and theresolution was observed. The thickness of this polyimide layer afterdrying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 80

The procedure was run the same way as Example 75.

25.78 g (80 mmol) of BTDA, 10.97 g (40 mmol) of3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane, 17.3 g (40mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 0.8 g (8 mmol) ofγ-valerolactone, 1.3 g (16 mmol) of pyridine, 205 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 3hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 50,300; Weight Average Molecular Weight(Mw): 226,600; Z Average Molecular Weight (Mz): 712,900; Mw/Mn=4.42;Mz/Mn=14.15.

EXAMPLE 81

The procedure was run the same way as Example 80.

17.77 g (40 mmol) of 6FDA, 5.49 g (20 mmol) of3,4-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane, 8.65 g (20mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 0.4 g (4 mmol) ofγ-valerolactone, 0.6 g (8 mmol) of pyridine, 122 g ofN-methylpyrrolidone and30 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for1.75 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 21,200; Weight Average Molecular Weight(Mw): 33,500; Z Average Molecular Weight (Mz): 48,500; Mw/Mn=1.58;Mz/Mn=2.28.

EXAMPLE 82

The procedure was run the same way as Example 80.

35.45 g (80 mmol) of 6FDA, 10.97 g (40 mmol) of3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane, 20.74 g(40 mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane, 0.8 g(8 mmol) of γ-valerolactone, 1.2 g (16 mmol) of pyridine, 286 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 3hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 64,300; Weight Average Molecular Weight(Mw): 129,100; Z Average Molecular Weight (Mz): 239,500; Mw/Mn=2.01;Mz/Mn=3.73.

EXAMPLE 83

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 28 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 28 Composition Components L LI LII Polyimide Solution Example 80Example 81 Example 82 Weight  15 g  15 g  15 g (Polyimide Content)   3 g  3 g   3 g 1,2-naphthoquinone-2- 0.9 g 0.9 g 0.9 g diazide-5-sulfonicacid-o- cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (L, LI and LII)was spin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layers were irradiated at a dose ofexposure of at which images are obtained, that is, irradiated with 300mJ of UV using 2 kW extra-high pressure mercury lamp apparatus(JP-2000G, commercial product of Oak Seisakusho). After irradiation,each coating layer was developed with the developer for 3.0 minutes(Composition L), 1.0 minute (Composition LI) or 1.5 minutes (CompositionLII). The developer was a mixture of 40 g of N-methylpyrrolidone, 10 gof aminoethanol, 25 g of methanol and 25 g of water. Each of the coatingmembrane after the irradiation was dipped in this solution for the timeperiod mentioned above, washed with deionized water, dried with aninfrared lamp, and the resolution was observed. The thickness of eachpolyimide layer after drying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 84

The procedure was run the same way as Example 78.

19.33 g (60 mmol) of BTDA, 3.67 g (30 mmol) of 2,4-diaminotoluene, 1.0 g(10 mmol) of γ-valerolactone, 1.2 g (15 mmol) of pyridine, 100 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture to room temperature, 9.67 g (30 mmol) of BTDA,8.23 g (30 mmol) of3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane, 12.32 g(30 mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}propane, 100 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 2hours. Then 60 g of N-methylpyrrolidone was added and the mixture washeated for another one hour, followed by addition of 2.5 g ofmorpholine. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 10% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 41,800; Weight Average Molecular Weight(Mw): 155,200; Z Average Molecular Weight (Mz): 414,100; Mw/Mn=3.71;Mz/Mn=9.90.

EXAMPLE 85

The procedure was run the same way as Example 78.

13.09 g (60 mmol) of pyromellitic dianhydride, 24.96 g (30 mmol) ofdiaminosilane (amine equivalent: 416), 1.0 g (10 mmol) ofγ-valerolactone, 1.2 g (15 mmol) of pyridine, 160 g ofN-methylpyrrolidone and 60 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 9.67 g (30 mmol) of BTDA,8.23 g (30 mmol) of3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane, 12.32 g(30 mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}propane, 100 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for3.15 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 37,600; Weight Average Molecular Weight(Mw): 83,200; Z Average Molecular Weight (Mz): 156,000; Mw/Mn=2.11;Mz/Mn=4.14.

EXAMPLE 86

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 29 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 29 Composition Components LIII LIV Polyimide Solution Example 84Example 85 Weight  30 g  15 g (Polyimide Content)   3 g   3 g1,2-naphthoquinone-2-diazide-5- 0.9 g 0.9 g sulfonic acid-o-cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (LIII and LIV)was spin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layers were irradiated at a dose ofexposure of at which images are obtained, that is, irradiated with 200mJ of UV using 2 kW extra-high pressure mercury lamp apparatus(JP-2000G, commercial product of Oak Seisakusho). After irradiation,each coating layer was developed with the developer for 90 seconds(Composition LIII) or 50 seconds (Composition LIV). The developer was amixture of 40 g of N-methylpyrrolidone, 10 g of aminoethanol, 25 g ofmethanol and 25 g of water. Each of the coating layer after theirradiation was dipped in this solution for the time period mentionedabove, washed with deionized water, dried with an infrared lamp, and theresolution was observed. The thickness of each polyimide layer afterdrying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 87

The procedure was run the same way as Example 75.

32.22 g (100 mmol) of BTDA, 13.72 g (50 mmol) of3,7-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane, 13.72 g(50 mmol) of 1,4-bis(3-aminopropyl)piperazine, 1.0 g (10 mmol) ofγ-valerolactone, 1.6 g (20 mmol) of pyridine, 309 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 200rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for1.5 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 15.4% by weight.

EXAMPLE 88

The procedure was run the same way as Example 78.

9.67 g (30 mmol) of BTDA, 8.23 g (30 mmol) of3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane, 12.32 g(30 mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}propane, 1.0 g (10 mmol)of γ-valerolactone, 1.6 g (20 mmol) of pyridine, 103 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 89 g ofN-methylpyrrolidone and 2.0 g of morpholine were added, and then 19.32 g(60 mmol) of BTDA, 3.0 g (15 mmol) of 1,4-bis(3-aminopropyl)piperazine,6.16 g (15 mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}propane, 119 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for2.45 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 19,700; Weight Average Molecular Weight(Mw): 30,700; Z Average Molecular Weight (Mz): 45,400; Mw/Mn=155;Mz/Mn=2.30.

EXAMPLE 89

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 30 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 30 Composition Components LV LVI Polyimide Solution Example 87Example 88 Weight  20 g  20 g (Polyimide Content)   3 g   3 g1,2-naphthoquinone-2-diazide-5- 0.9 g 0.9 g sulfonic acid-o-cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (LV and LVI) wasspin-coated on 5 cm diameter of surface-treated copper foil (commercialproduct of Nippon Denkai, 18 μm thickness). Thereafter, the coated layerwas dried at 90° C. for 10 minutes in an infrared oven. The thickness ofthis photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced and all of the coating layer were irradiated at a dose ofexposure of at which images are obtained, that is, irradiated with 100mJ (Composition LV) or with 200 mJ (Composition LVI) of UV using 2 kWextra-high pressure mercury lamp apparatus (JP-2000G, commercial productof Oak Seisakusho). After irradiation, each coating layer was developedwith the developer for 35 seconds. The developer was a mixture of 40 gof N-methylpyrrolidone, 10 g of aminoethanol, 25 g of methanol and 25 gof water. Each of the coating layer after the irradiation was dipped inthis solution for the time period mentioned above, washed with deionizedwater, dried with an infrared lamp, and the resolution was observed. Thethickness of each polyimide layer after drying at 90° C. for 30 minuteswas 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 90

A condenser tube with a ball, having a water separation trap, wasmounted on a 1-liter separable three-necked flask equipped with ananchor-shaped stirrer made of stainless steel 26.66 g (60 mmol) of 6FDA,17.3 g (40 mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 7.21 g (20mmol) of 9,10-bis(4-aminophenyl)anthraquinone (Wakayama Seika Co., Ltd.,hereinafter referred to as “ADA”), 0.6 g (6 mmol) of γ-valerolactone,1.0 g (12 mmol) of pyridine, 196 g of N-methylpyrrolidone and 30 g oftoluene were added. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 μminutes, the mixture washeated at 180° C. and stirred at 180 rpm for 2.50 hours. In thereaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 31,700; Weight Average Molecular Weight(Mw): 49,400; Z Average Molecular Weight (Mz): 72,400; Mw/Mn=1.56;Mz/Mn=2.29.

EXAMPLE 91

The procedure was run the same way as Example 90.

19.33 g (60 mmol) of BTDA, 17.3 g (40 mmol) ofbis(4-(3-aminophenoxy)phenyl}sulfone, 7.21 g (20 mmol) of ADA, 0.6 g (6mmol) of γ-valerolactone, 1.0 g (12 mmol) of pyridine, 236 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for2.5 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 15% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 47,100; Weight. Average Molecular Weight(Mw): 135,600; Z Average Molecular Weight (Mz): 347,000; Mw/Mn=2.88;Mz/Mn=7.28.

EXAMPLE 92

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 31 below and filtering the mixtures through a filter having 3μm diameter of

TABLE 31 Composition Components LVII LVIII Polyimide Solution Example 90Example 91 Weight  15 g  20 g (Polyimide Content)   3 g   3 g1,2-naphthoquinone-2-diazide-5- 0.9 g 0.9 g sulfonic acid-o-cresol ester

(2) Formation of Images

Each of the above-described photosensitive compositions (LVII and LVIII)was spin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the layers were irradiated at a dose of exposure ofat which images are obtained using 2 kW extra-high pressure mercury lampapparatus (JP-2000G, commercial product of Oak Seisakusho). Afterirradiating the coating layer under the conditions shown in Table 32,each coating layer was developed with the developer under the conditionsshown in Table 32.

TABLE 32 Composition LVII LVIII Dose of Irradiated UV Light (mJ) 500 300Development Time (minute)  3 6.3

The developer was a mixture of 40 g of N-methylpyrrolidone, 10 g ofaminoethanol, 25 g of methanol and 25 g of water. Each of the coatinglayer after the irradiation was dipped in this solution for the timeperiod mentioned above, washed with deionized water, dried with aninfrared lamp, and the resolution was observed. The thickness of eachpolyimide coating membrane after drying at 90° C. for 30 minutes was 9μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 93

The procedure was run as the same way as Example 90.

14.89 g (60 mol) of BTDA, 3.67 g (30 mmol) of 2,6-diaminotoluene, 0.9 g(9 mmol) of γ-valerolactone; 1.0 g (12 mmol) of pyridine, 100 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 9.67 g (30 mmol) of BTDA,12.98 g (30 mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 10.82 g (30mmol) of ADA, 95 g of N-methylpyrrolidone and 10 g of toluene wereadded. After stirring the mixture at 180 rpm at room temperature undernitrogen atmosphere for 60 minutes, the mixture was heated at 180° C.and stirred at 180 rpm for 2.15 hours; In the reaction, toluene-waterazeotrope was removed. After the reaction, 100 g of N-methylpyrrolidonewas added.

The polymer concentration thus obtained was 14% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 18,600; Weight Average Molecular Weight(Mw): 80,700; Z Average Molecular Weight (Mz): 342,200; Mw/Mn=4.34;Mz/Mn=18.42.

EXAMPLE 94

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 19 g of thepolyimide solution obtained in Example 93 (polyimide content: 2.7 g) and0.8 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester.

(2) Formation of Images

Images were formed using the photosensitive composition in the samemanner as in Example 92 except that the dose of irradiated UV light was300 mJ, the development time was 6 minutes, and that the developer was amixture of 40 g of N-methylpyrrolidone, 10 g of aminoethanol, 25 ofmethanol and 25 of water. The coating layer after irradiation with UVlight was dipped in this solution for the time period mentioned above,washed with deionized water, dried with an infrared lamp, and theresolution was observed. The thickness of this polyimide layer afterdrying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 95

The procedure was run the same way as Example 93.

14.89 g (40 mmol) of bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylicdianhydride, 6.01 g (30 mmol) of 3,4′-diamino-biphenyl ether, 0.6 g (6mmol) of γ-valerolactone, 1.0 g (12 mmol) of pyridine, 100 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 13.33 g (30 mmol) of6FDA, 21.26 g (41 mmol) of2,2-bis{4-(3-aminophenoxy)phenyl}hexafluoropropane, 6.96 g (19 mmol) ofADA, 137 g of N-methylpyrrolidone and 10 g of toluene were added. Afterstirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 60 minutes, the mixture was heated at 180° C. and stirredat 180 rpm for 2.15 hours. In the reaction, toluene-water azeotrope wasremoved.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 62,100; Weight Average Molecular Weight(Mw): 35,000; Z Average Molecular Weight (Mz): 123,300; Mw/Mn=2.00;Mz/Mn=13.53.

EXAMPLE 96

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared as in Example 92 using thepolyimide solution obtained in Example 95.

(2) Formation of Images

Images were formed using the photosensitive layer in the same manner asin Example 92 except that the dose of irradiated UV light was 300 mJ,the development time was 8.45 minutes, and that the developer was amixture of 40 g of N-methylpyrrolidone, 10 g of aminoethanol, 25 ofmethanol and 25 of water. The photosensitive layer after irradiationwith UV light was dipped in this solution for the time period mentionedabove, washed with deionized water, dried with an infrared lamp, and theresolution was observed: The thickness of this polyimide layer afterdrying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 97

A condenser tube with a ball, having a water separation trap, wasmounted on a one-liter separable three-necked flask equipped with ananchor-shaped stirrer made of stainless steel. The flask was dipped in asilicone bath to heat the flask under stirring and under nitrogen gasflow, 58.845 g (200 mol) of BPDA, 43.25 g (100 mmol) ofbis-{4-(3-aminophenoxy)phenylsulfone (commercial product of WakayamaSeika Co., Ltd.), 51.85 g (100 mmol) of2,2-bis{4-(3-aminophenoxy)phenyl}hexafluoropropane (commercial productof Wakayama Seika Co., Ltd.), 2.0 g (20 mmol) of γ-valerolactone, 3.2 g(40 mmol) of pyridine, 587 g of N-methylpyrrolidone and 50 g of toluenewere added. After stirring the mixture at 200 rpm at room temperatureunder nitrogen atmosphere for 30 minutes, the mixture was heated at 180°C. (bath temperature) and stirred at 180 rpm for 3 hours. While removingthe toluene-water azeotrope accumulated in the trap, the reactioncompleted.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 52,600; Weight Average Molecular Weight(Mw): 80,300; Z Average Molecular Weight (Mz): 105,800; Mw/Mn=1.53;Mz/Mn=2.01.

EXAMPLE 98

The procedure was run the same way as Example 1.

A condenser tube with a ball, having a water separation trap, wasmounted on a 0.5L separable three-necked flask equipped with ananchor-shaped stirrer made of stainless steel. In the flask, 26.48 g (90mmol) of BPDA, 12.98 g (30 mmol) ofbis{4-(4-aminophenoxy)phenyl}sulfone, 14.90 g (60 mmol) of4,4′-diaminodiphenylsulfone, 1.0 g (10 mmol) of γ-valerolactone, 1.7 g(20 mmol) of pyridine, 205 g of N-methylpyrrolidone and 50 g of toluenewere added. After stirring the mixture at 180 rpm at room temperatureunder nitrogen atmosphere for 30 minutes, the mixture was heated at 180°C. and stirred at 180 rpm for 3 hours. In the reaction, toluene-waterazeotrope was removed.,

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 18,700; Weight Average Molecular Weight(Mw): 29,300; Z Average Molecular Weight.(Mz): 39,700; Mw/Mn=1.52;Mz/Mn=2.13.

EXAMPLE 99

The procedure was run the same way as Example 97.

26.48 g (90 mmol) of BPDA, 12.32 g (30 mmol) of2,2-bis-4(4′-aminophenoxy)phenylpropane (commercial product of WakayamaSeika Co., Ltd.), 14.90 g (60 mmol) of 4,4′-diaminodiphenylsulfone, 1.0g (10 mmol) of γ-valerolactone, 1.2 g (15 mmol) of pyridine, 182 g ofN-methylpyrrolidone and 40 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 3hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 33,300; Weight Average Molecular Weight(Mw): 43,400; Z Average Molecular Weight (Mz): 55,400; Mw/Mn=1.30;Mz/Mn=1.66.

EXAMPLE 100

The procedure was run the same way as Example 97.

96.67 g (300 mmol) of BPDA, 47.58 g (110 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone, 178 g (200 mmol) ofbis(3,3′-diaminopropyl)silane (commercial product of Shin-etsu ChemicalCo., Ltd., amine equivalent: 890), 3.28 g (20 mmol) of5-norbornane-2,3-dicarboxylic dianhydride, 3.0 g (30 mmol) ofγ-valerolactone, 4.0 g (50 mmol) of pyridine, 473 g ofN-methylpyrrolidone and 100 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180rpm for 5.5hours. In the reaction, toluene-water azeotrope was removed. After thereaction, 73 g of benzyl alcohol was added.

The polymer concentration thus obtained was 40% by; weight. Themolecular weights based on polystyrene measured as in Example 1 were:Number Average Molecular Weight (Mn): 22,800; Weight Average MolecularWeight (Mw): 41,400; Z Average Molecular Weight (Mz): 67,000;Mw/Mn=1.81; Mz/Mn=2.44.

EXAMPLE 101

The procedure was run the same way as Example 1.

13.09 g (60 mmol) of pyromellitic dianhydride, 14.89 g (60 mmol) ofbicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (commercialproduct of Aldrich), 61.9 g (120 mmol) ofbis-4-{(3-aminophenoxy)phenyl}sulfone, 1.2 g (12 mmol) ofγ-valerolactone, 1.12 g (24 mmol) of pyridine, 302 g ofN-methylpyrrolidone and 50 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for3.75 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 71,100; Weight Average Molecular Weight(Mw): 113,600; Z Average Molecular Weight (Mz): 167,200; Mw/Mn=1.60;Mz/Mn=2.35.

EXAMPLE 102

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 33 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 33 Composition Components LIX LX LXI LXII LXIII Polyimide SolutionEx. 97 Ex. 98 Ex. 99 Ex. 100 Ex. 101 Weight  15 g  15 g  15 g 7.5 g  15g (Polyimide Content)   3 g   3 g   3 g   3 g   3 g naphthoquinonediazide- 0.9 g 0.9 g 0.9 g 0.9 g 0.9 g 1,2,5-o-cresol ester

(2) Formation of Images

Each of the above-described 5 photosensitive compositions wasspin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive coating layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and the coating layer was irradiated at a dose of exposure atwhich images are obtained shown in Table 34 below using 2 kW extra-highpressure mercury lamp apparatus (JP-2000G, commercial product of OakSeisakusho).

TABLE 34 Composition LIX LX LXI LXII LXIII Dose of Irradiated UV Light(mJ) 300 500 500 300 200 Development Time (minute) 4.5 3.15 2.3 6.3 1.1

The developer was a mixture of 40 g of N-methylpyrrolidone, 10 g ofaminoethanol, 25 g of methanol and 25 g of water. Each of the coatinglayer after irradiation with UV light was dipped in this solution forthe time period mentioned above, washed with deionized water, dried withan infrared lamp, and the resolution was observed. The thickness of thispolyimide layer after drying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

This polyimide coating layer was heated with infrared light at 150° C.for 30 minutes. After this heat treatment, the thickness of the membranewas 8 μm, so that the thickness was not substantially changed. Thepolyimide coating layer was then heated with infrared light at 260° C.for 30 minutes, and the thickness of the layer became 6 μm. The adhesionbetween the polyimide layer and the copper foil was evaluated by crosscut test. The coating layer was cross cut with a knife such that eachlattice had a size of 1 mm×1 mm and was tried to peeled off with acellophane-tape. As a result, 100/100 lattices remained adhered (nolattices peeled off), so that the adhesion between the polyimide layerand the copper foil was sufficiently high, which can be used inpractice.

EXAMPLE 103

The procedure was run the same way as Example 97.

38.62 g (120 mmol) of BTDA, 7.33 g (60 mmol) of diaminotoluene, 1.8 g(18 mmol) of γ-valerolactone, 2.4 g (36 mmol) of pyridine, 100 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 80 rpm for 1hour. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 12.32 g (30 mmol) ofbis-4-{(3-aminophenoxy)phenyl}sulfone, 12.96 g (30 mmol) of2,2-bis-4(4′-aminophenoxy)phenylpropane, 94 g of N-methylpyrrolidone and20 g of toluene were added. After stirring the mixture at 180 rpm atroom temperature under nitrogen atmosphere for 30 minutes, the mixturewas heated at 180° C. and stirred at 180 rpm for 2.8 hours. In thereaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 25% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 36,000; Weight Average Molecular Weight(Mw): 158,800; Z Average Molecular Weight (Mz): 559,200; Mw/Mn=4.40;Mz/Mn=15.52.

EXAMPLE 104

The procedure was run the same way as Example 103.

Under nitrogen gas flow, 38.67 g (120 mmol) of BTDA, 25.95 g (60 mmol)of bis-4-{(3-aminophenoxy)phenyl}sulfone, 1.8 g (18 mmol) ofγ-valerolactone, 2.9 g (36 mmol) of pyridine, 200 g ofN-methylpyrrolidone and 40 g of toluene were added to the flask. Afterstirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 30 minutes, the mixture was heated at 180° C. and stirredat 180 rpm for 1 hour. In the reaction, toluene-water azeotrope wasremoved.

After cooling the mixture at room temperature, 17.65 g (60 mmol) ofBPDA, 12.01 g (60 mmol) of 3,4′-diaminodiphenyl ether, 24.63 g (60 mmol)of 2,2-bis-4(4′-aminophenoxy)phenylpropane, 250 g of N-methylpyrrolidoneand 20 g of toluene were added. After stirring the mixture at 180 rpm atroom temperature under nitrogen atmosphere for 30 minutes, the mixturewas heated at 180° C. and stirred at 180 rpm for 3 hours. In thereaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 25% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh. Corporation) were: NumberAverage Molecular Weight (Mn): 39,700; Weight Average Molecular Weight(Mw): 113,800; Z Average Molecular Weight (Mz): 270,000; Mw/Mn=2.86;Mz/Mn=6.80.

EXAMPLE 105

The procedure was run the same way as Example 103.

Under nitrogen gas flow, 48.34 g (150 mmol) of BTDA, 9.165 g (75 mmol)of 2,4-diaminotoluene, 1.5 g (15 mmol) of γ-valerolactone, 1.78 g (30mmol) of pyridine, 130 g of N-methylpyrrolidone and 70 g of toluene wereadded to the flask. After stirring the mixture at 180 rpm at roomtemperature under nitrogen atmosphere for 30 minutes, the mixture washeated at 180° C. and stirred at 180 rpm for 1.3 hours. In the reaction,toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 32.44 g (75 mmol) ofbis-4-{(3-aminophenoxy)phenyl}sulfone, 67 g of N-methylpyrrolidone and40 g of toluene were added. After stirring the mixture at 180 rpm atroom temperature under nitrogen atmosphere for 30 minutes, the mixturewas heated at 180° C. and stirred at 180 rpm for 4.5 hours. In thereaction, toluene-water azeotrope was removed. After the reaction, 52 gof N-methylpyrrolidone was added.

The polymer concentration thus obtained was 25% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 21,900; Weight Average Molecular Weight(Mw): 59,000; Z Average Molecular Weight (Mz): 146,600; Mw/Mn=2.70;Mz/Mn=6.71.

EXAMPLE 106

(1) Preparation of Photosensitive Compositions

Photosensitive compositions were prepared by mixing the components shownin Table 35 below and filtering the mixtures through a filter having 3μm diameter of pores.

TABLE 35 Composition Components LXIV LXV LXVI Polyimide Solution Example103 Example 104 Example 105 Weight  20 g  20 g  20 g (Polyimide Content)  5 g   5 g   5 g naphthoquinone diazide-1,2,5- 1.5 g 1.5 g 1.5 go-cresol ester

(2) Formation of Images

Each of the above-described 3 photosensitive compositions wasspin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive coating layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layers were irradiated at a dose ofexposure of at which images are obtained, that is, irradiated with 300mJ of UV using 2 kW extra-high pressure mercury lamp apparatus(JP-2000G, commercial product of Oak Seisakusho). Thereafter, eachcoating layer was developed in the developer for 2.0 minutes(Composition LXIV), 2.8 minutes (Composition LXV) and 0.15 minutes(Composition LXVI). The developer was a mixture of 40 g ofN-methylpyrrolidone, 25 g of aminoethanol, 25 g of methanol and 10 g ofwater. Each of the coating layer after the irradiation was dipped inthis solution for the time period mentioned above, washed with deionizedwater, dried with an infrared lamp, and the resolution was observed. Thethickness of each polyimide layer after drying at 90° C. for 30 minuteswas 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed withCompositions F and G, and formation of images of lines having a width of15 μm was confirmed with Composition H.

EXAMPLE 107

A condenser tube with a ball, having a water separation trap, wasmounted on a one-liter separable three-necked flask equipped with ananchor-shaped stirrer made of stainless steel. Under nitrogen gas flow,in the flask, 6.44 g (20 mmol) of BTDA, 6.09 g (40 mmol) of3,5-diaminobenzoic acid (hereinafter referred to as “DABZ”), 0.6 g (6mmol) of γ-valerolactone, 3.2 g (40 mmol) of pyridine, 60 g of,N-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 200 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 3hours. In the reaction, toluene-water azeotrope was removed. Then 192 gof N-methylpyrrolidone was added.

After cooling the mixture at room temperature, 17.77g (40 mmol) of 6FDA,10.37 g (20 mmol) of 2,2-bis{4-(4-aminophenoxy)phenyl}hexafluoropropane,94 g of N-methylpyrrolidone and 10 g of toluene were added. Afterstirring the mixture at 180 rpm at room temperature under nitrogenatmosphere for 0.5 hours, the mixture was heated at 180° C. and stirredat 180 rpm for 2.7 hours. In the reaction, toluene-water azeotrope wasremoved.

Further, after cooling the mixture at room temperature, 3.8 g (40 mmol)of morpholine and 10 g of N-methylpyrrolidone were added and the mixturewas stirred for 30 minutes, followed by stirring the mixture at 130° C.at 130 rpm for 1 hour to carry out the reaction.

The polymer concentration thus obtained was 10% by weight. The molecularweights based on polystyrene measured by high performance liquidchromatography (commercial product of.Tosoh Corporation) were: NumberAverage Molecular Weight (Mn): 13,400; Weight Average Molecular Weight(Mw): 23,700; Z Average Molecular Weight (Mz): 37,300; Mw/Mn=1.77;Mz/Mn=2.79.

By making the reaction time of the second step longer than 2.7 hours,the Mw became not less than 50,000.

EXAMPLE 108

The procedure was run the same way as Example 107.

6.44 g (20 mmol) of BTDA, 6.09 g (40 mmol) of DABZ, 0.6 g (6 mmol) ofγ-valerolactone, 3.2 g (40 mmol) of pyridine, 60 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 12.89 (40 mmol) of BTDA,8.21 g (20 mmol) of2,2-bis{4-(4-aminophenoxy)phenyl}propane, 223 g ofN-methylpyrrolidone and 10 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 0.5hours, the mixture was heated at 180° C. and stirred at 180 rpm for 2.7hours. In the reaction, toluene-water azeotrope was removed.

Further, after cooling the mixture at room temperature, 4.41 g (44 mmol)of N-methylpiperazine and 10 g of N-methylpyrrolidone were added and themixture was stirred for 30 minutes, followed by stirring the mixture at120° C. at 120 rpm for 1 hour to carry out the reaction.

The polymer concentration thus obtained was 10% by weight. Since thispolyimide was not soluble in dimethylformamide, the molecular weightthereof could not be measured.

EXAMPLE 109

(1) Preparation of Photosensitive Compositions

A photosensitive composition LXVII (Example 107) and a photosensitivecomposition LXVIII (Example 108) were prepared by mixing 30 g of thepolyimide solution obtained in Example 107 or 108 (the polyimide contentin both solutions was 3 g) with 0.9 g of1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester.

(2) Formation of Images

Each of the above-described 2 photosensitive compositions wasspin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared hot airdryer., The thickness of this photosensitive layer was about 10 μm.

On this photosensitive coating layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layers were irradiated at a dose ofexposure of at which images are obtained using 2 kW extra-high pressuremercury lamp apparatus (JP-2000G, commercial product of Oak Seisakusho).

Composition LXVII was irradiated with 500 mJ and then developed underthe following conditions. The developer was a mixture of 40 g ofN-methylpyrrolidone, 10 g of aminoethanol, 25 g of methanol and 25 g ofwater. The coating layer after the irradiation was dipped in thissolution for 3 minutes, washed with deionized water, dried with aninfrared lamp, and the resolution was observed. The thickness of eachpolyimide layer after drying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

Composition LXVIII was irradiated with 500 mJ and then developed underthe following conditions. The developer was a mixture of 40 g ofN-methylpyrrolidone, 10 g of aminoethanol, 25 g of methanol and 25 g ofwater. The coating layer after the irradiation was dipped in thissolution for 1.5 minutes, washed with deionized water, dried with aninfrared lamp, and the resolution was observed. The thickness of eachpolyimide layer after drying at 90° C. for 30 minutes was 9 μm.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 10 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 10 μm was confirmed.

EXAMPLE 110

The procedure was run the same way as Example 107.

17.77 g (40 mmol) of 6FDA, 3.04 g (20 mmol) of DABZ, 6.01 g (30 mmol) of4,4′-diaminodiphenyl ether, 0.8 g (8 mmol) of γ-valerolactone, 1.3 g (16mmol) of pyridine, 107 g of N-methylpyrrolidone and 25 g of toluene wereadded. After stirring the mixture at 180 rpm at room temperature undernitrogen atmosphere for 30 minutes, the mixture was heated at 180° C.and stirred at 180 rpm for 2 hours: In the reaction, toluene-waterazeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 14,800; Weight Average Molecular Weight(Mw): 25,400; Z Average Molecular Weight (Mz): 62,500; Mw/Mn=1.71;Mz/Mn=4.21.

EXAMPLE 111

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing; 15 g of thepolyimide solution obtained in Example 110 (polyimide content: 3 g) with0.9 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester.

(2) Formation of Images

The photosensitive composition prepared in (1) was spin-coated on 5 cmdiameter of a surface-treated copper foil (commercial product of.NipponDenkai, 18 m thickness). Thereafter, the coated layer was dried at 90°C. for 10 minutes in an infrared oven. The thickness of thisphotosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layers were irradiated at a dose ofexposure of at which images are obtained using 2 kW extra-high pressuremercury lamp apparatus (JP-2000G, commercial product of Oak Seisakusho).

The photosensitive layer was irradiated with 300 mJ and then developedunder the following conditions. The developer was a mixture of 30 g ofaminoethanol, 50 g of ethanol and 15 g of water. The coating layer afterthe, irradiation was dipped in this solution for 1.25 minutes, washedwith deionized water, dried with an infrared lamp, and the resolutionwas observed. As a result, although the sharpness was little bit poor,images corresponding to the pattern were observed.

The photosensitive layer was also irradiated with 500 mJ and thendeveloped under the following conditions. The developer was a mixture of40 g of N-methylpyrrolidone, 10 g of aminoethanol, 25 g of ethanol and1.5 g of water. The coating layer after the irradiation was dipped inthis solution for 2.5 minutes, washed with deionized water, dried withan infrared lamp, and the resolution was observed. As a result, althoughthe sharpness was little bit poor, images corresponding to the patternwere observed.

EXAMPLE 112

The procedure was run the same way as Example 107.

24.82 g (100 mmol) of bicyclo-(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylicdianhydride, 7.61 g (50 mmol) of DABZ; 1.5 g (15 mmol) ofγ-valerolactone, 2.4 g (30 mmol) of pyridine, 120 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 1hour. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 14.71 g (50 mmol) of3,4,3′,4′-biphenyltetracarboxylic dianhydride, 10.01 g (50 mmol) of3,4′-diaminodiphenyl ether, 20.53 g (50 m mol) of2,2-bis-{4-(4-aminophenoxy)phenylpropane, 109 g of N-methylpyrrolidoneand 30 g of toluene were added. After stirring the mixture at 180 rpm atroom temperature under nitrogen atmosphere for 0.5 hours, the mixturewas heated at 180° C. and stirred at 180 rpm for 2 hours. In thereaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 46,700; Weight Average Molecular Weight(Mw): 102,600; Z Average Molecular Weight (Mz): 82,400; Mw/Mn=2.20;Mz/Mn=3.90.

EXAMPLE 113

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 15 g of thepolyimide solution obtained in Example 112 (polyimide, content: 3 g)with 0.9 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresolester.

(2) Formation of Images

The photosensitive composition prepared in (1) was spin-coated on 5 cmdiameter of a surface-treated copper foil (commercial product of NipponDenkai, 18 μm thickness). Thereafter, the coated layer was dried at 90°C. for 10 minutes in an infrared oven. The thickness of thisphotosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layers were irradiated at a dose ofexposure of at which images are obtained using 2 kW extra-high pressuremercury lamp apparatus (JP-2000G, commercial product of Oak Seisakusho).

The photosensitive layer was irradiated with 300 mJ and then developedunder the following conditions. The developer was a mixture of 30 g ofaminoethanol, 50 g of ethanol and 15 g of water. The coating layer afterthe irradiation was dipped in this solution for 6 minutes, washed withdeionized water, dried with an infrared lamp, and the resolution wasobserved. As a result, although the sharpness was little bit poor,images corresponding to the pattern were observed.

EXAMPLE 114

The procedure was run the same way as Example 110.

11.11 g (50 mmol) of BTDA, 3.80 g of DABZ, 10.81 g (25 mmol) ofbis{4-(3-aminophenoxy)phenyl}sulfone, 1.0 g (10 mmol) ofγ-valerolactone, 2.9 g (30 mmol) of pyridine, 106 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for30minutes, the-mixture was heated at 180° C. and stirred at 180 rpm for 3hours. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 2.61 g (30 mmol) ofmorpholine and 210 g of N-methylpyrrolidone were added. After stirringthe mixture at 180 rpm at room temperature under nitrogen atmosphere for0.5 hours, the mixture was heated at 160° C. and stirred at 180 rpm for1 hour. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 13,100; Weight Average Molecular Weight(Mw): 22,400; Z Average Molecular Weight (Mz): 36,700; Mw/Mn=1.71;Mz/Mn=2.65.

EXAMPLE 115

The procedure was run the same way as Example 1.

29.00 g (90 mmol) of BTDA, 6.85 g (45 mmol) of DABZ, 19.46 g (45 mmol)of bis{4-(3-aminophenoxy)phenyl}sulfone, 0.9 g (9 mmol) ofγ-valerolactone, 3.6 g (45 mmol) of pyridine, 208 g ofN-methylpyrrolidone and 30 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for 2hours. In the reaction, toluene-water azeotrope was removed.

After cooling the mixture at room temperature, 5.41 g (54 mmol) ofN-methylpiperizine and 10 g of toluene were added. The mixture wasstirred at 160 rpm at room temperature under nitrogen atmosphere for 1.3hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 20% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 5200; Weight Average Molecular Weight(Mw): 8900; Z Average Molecular Weight (Mz): 13,000; Mw/Mn=1.71;Mz/Mn=2.50.

EXAMPLE 116

(1) Preparation of Photosensitive Compositions

A photosensitive composition LXIX (Example 114) and a photosensitivecomposition LXX (Example 115) were prepared by mixing 15 g of thepolyimide solution obtained in Example 114 or 115 (the polyimide contentin both solutions was 3 g) with 0.9 g of1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester.

(2) Formation of Images

Each of the above-described 2 photosensitive compositions wasspin-coated on 5 cm diameter of a surface-treated copper foil(commercial product of Nippon Denkai, 18 μm thickness). Thereafter, thecoated layer was dried at 90° C. for 10 minutes in an infrared oven. Thethickness of this photosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating layer were irradiated at a dose ofexposure of at which images are obtained using 2 kW extra-high pressuremercury lamp apparatus (JP-2000G, commercial product of Oak Seisakusho).

Each of these layers was irradiated with 300 mJ and then developed underthe following conditions. The developer was a mixture of 30 g ofaminoethanol, 50 g of ethanol and 15 g of water. The coating layers madeof Composition LXIX after the irradiation was dipped in this solutionfor 15 seconds, and Composition LXX after the irradiation was dipped inthis solution for 2.5 minutes. Each of the coating layers was thenwashed with deionized water, dried with an infrared lamp, and theresolution was observed.

As for the through hole patterns in the coating polyimide layer,formation of through holes having sharp and circular sections having adiameter of 15 μm was confirmed. As for the line-and-space pattern,formation of images of lines having a width of 15 μm was confirmed.

EXAMPLE 117

The procedure was run the same way as Example 107.

96.67 g (300 mmol) of BTDA, 22.82 g (150 mmol) of DABZ, 64.88 g (150mmol) of bis{4-(3-aminophenoxy)phenyl}sulfone, 3.0 g (30 mmol) ofγ-valerolactone, 12 g (150 mmol) of pyridine, 405 g ofN-methylpyrrolidone and 50 g of toluene were added. After stirring themixture at 180 rpm at room temperature under nitrogen atmosphere for 30minutes, the mixture was heated at 180° C. and stirred at 180 rpm for2.7 hours. In the reaction, toluene-water azeotrope was removed.

The polymer concentration thus obtained was 30% by weight. The molecularweights based on polystyrene measured as in Example 1 were: NumberAverage Molecular Weight (Mn): 20,100; Weight Average Molecular Weight(Mw): 42,700; Z Average Molecular Weight (Mz): 19,800; Mw/Mn=2.12;Mz/Mn=3.97.

EXAMPLE 118

(1) Preparation of Photosensitive Composition

A photosensitive composition was prepared by mixing 10 g of thepolyimide solution obtained in Example 117 (polyimide content: 3 g) with0.9 g of 1,2-naphthoquinone-2-diazide-5-sulfonic acid-o-cresol ester.

(2) Formation of Images

The photosensitive composition prepared in (1) was spin-coated on 5 cmdiameter of a surface-treated copper foil (commercial product of NipponDenkai, 18 μm thickness). Thereafter, the coated layer was dried at 90°C. for 10 minutes in an infrared oven. The thickness of thisphotosensitive layer was about 10 μm.

On this photosensitive layer, a test pattern (through holes andline-and-space pattern having diameters and widths of 10, 15, 20,25, - - - , and 200 μm, respectively) for positive-type photomask wasplaced, and all of the coating membranes were irradiated at a dose ofexposure of at which images are obtained using 2 kW extra-high pressuremercury lamp apparatus (JP-2000G, commercial product of Oak Seisakusho).

The photosensitive layer was irradiated with 300 mJ and then developedunder the following conditions. The developer was a mixture of 30 g ofaminoethanol, 50 g of ethanol and 15 g of water. The coating layer afterthe irradiation was dipped in this solution for 6.5 minutes, washed withdeionized water, dried with an infrared lamp, and the resolution wasobserved.

The through hole pattern obtained with this polyimide coating layer waslittle bit poor in contrast, but images corresponding to the patternwere observed.

INDUSTRIAL AVAILABILITY

As described above, according to the present invention, thesolvent-soluble polyimides obtained by the direct polycondensation ofaromatic dianhydrides and aromatic diamines in the presence of an acidcatalyst gave very good image resolutions by irradiating the polyimidesin the presence of a photoacid generator. In cases where thephotosensitive polyimide of the present invention is used as a heatresistant insulative membrane, the polyimide having a molecular weightof 25,000 to 200,000 is made into insulative membranes having hightemperature heat resistance, electric insulation and adhesiveness, sothat it can be widely used in the field of production of semiconductorsand electronic parts.

What is claimed is:
 1. Positive-type photosensitive polyimidecompositions comprising a photoacid generator and a solvent-solublepolyimide (excluding those having phenolic hydroxyl group, carboxylgroup, thiophenol group, or sulfonic acid group, or a derivative of anyof said groups which yields any of said groups by action of saidphotoacid generator) which shows positive photosensitivity in thepresence of said photoacid generator, wherein said polyimide is formedby polycondensation between one or more tetracarboxylic dianhydrides andone or more aromatic diamines, wherein one of the aromatic diaminecomponents is dialkyl-diamino-biphenyl sulfone.
 2. The compositionaccording to claim 1, wherein said polyimide contains a photosensitivearomatic diamine and/or an aromatic diamine which is made soluble in analkali by an acid generated by photolysis.
 3. The composition accordingto claim 2, wherein said photosensitive aromatic diamine is at least oneselected from the group consisting of 4,4′-diaminodiphenyl sulfone,3,3′-diaminodiphenyl sulfone, bis{4,4-aminophenoxy)phenyl}sulfone,bis{4-(3-aminophenoxy)phenyl}sulfone, o-tolidine sulfone,4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl disulfide,4,4′-diaminobenzophenone 3,3′-diaminobenzophenone,1,5-diaminoanthraquinone, 2-nitro-1,4-diaminobenzene,3,3′-dinitro-4,4′-diaminobiphenyl, 1,5-diaminonaphthalene,9,9-bis(4-aminophenyl)fluorene and 9,10-bis(4-aminophenyl)anthracene. 4.The composition according to any one or claims 1 to 3, wherein saidpolyimide contains at least one aromatic diamine component selected fromthe group consisting of 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylether, bis(4-phenoxy)1,4-benzene, bis(3-phenoxy)1,4-benzene,bis(3-phenoxy)1,3-benzene, 2,2-bis(4-aminophenyl)propane,1,1,1,3,3,3-hexafluoro-2-bis(4-aminophenyl)propane,4,4′-diaminodiphenylmethane, bis(4-aminophenoxy)4,4′-diphenyl,2,2-bis{(4-aminophenoxy)phenyl}propane2,2-bis{(4-aminophenoxy)phenyl}hexafluoropropane, 1,3-diaminobenzene,1,4-diaminobenzene, 2,4-diaminotoluene,3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)benzidine,α,α-bis(4-aminophenyl)-1,4-diisopropylbenzene,bis(4-aminophenoxy)-1,3-(2,2-dimethyl)propane and diaminosiloxane. 5.The composition according to claim 4, wherein said polyimide contains asan acid component at least one acid component selected from the groupconsisting of 3,4,3′,4′-benzophenone tetracarboxylic dianhydride,3,4,3′,4,-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride2,3,3′,4′-biphenyl ether tetracarboxylic dianhydride,1,2,5,6-naphthalene carboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, biphenyl sulfone tetracarboxylicdianhydride, bicyclo(2,2,2)-oct-ene-2,3,5,6-tetracarboxylic dianhydrideand4,4′-{2,2,2-trifluoro-1-(trifluoromethyl)ethylidene}bis(1,2-benzenedicarboxylicdianhydride).
 6. The composition according to any one of claims 1 to 3,wherein said polyimide contains at least one acid component selectedfrom the group consisting of 3,4,3′,4′-benzophenone tetracarboxylicdianhydride, 3,4,3′,4′-biphenyltetracarboxylic dianhydride, pyromelliticdianhydride 2,3,3′,4′-biphenyl ether tetracarboxylic dianhydride,1,2,5,6-naphthalene carboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,3′,4′-biphenyl sulfone tetracarboxylicdianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylicdianhydride and4,4′-{2,2,2-trifluoro-1-(trifluoromethyl)ethylidene}bis(1,2-benzenedicarboxylicdianhydride).
 7. The composition according to claim 1, wherein saiddialkyl-diamino-biphenyl sulfone is 3,3′-dimethyl-4,4′-diamino-biphenylsulfone.
 8. The composition according to any one of claims 1 to 3,wherein said polyimide contains 9,9-bis(aminophenyl) fluorene and/or9,9-bis(aminoalkyl-phenyl)fluorene as one of the aromatic diaminecomponents.
 9. The composition according to claim 8, wherein said9,9-bis(aminophenyl)fluorene and/or 9,9-bis(aminoalkyl-phenyl)fluoreneis 9,9-bis(4-aminophenyl)fluorene and/or9,9-bis(3-methyl-4-aminophenyl)fluorene.
 10. The composition accordingto any one of claims 1 to 3, wherein said polyimide containsdiaminopyridine and/or diaminoacridinium as one of the aromatic diaminecomponents.
 11. The composition according to claim 10, wherein saiddiaminopyridine and/or diaminoacridinium is 2,6-diaminopyridine and/oracriflavine.
 12. The composition according to any one of claims 1 to 3,wherein said polyimide contains 1,5-diaminoanthraquinone as one of thearomatic diamines.
 13. The composition according to any one of claims 1to 3, wherein said polyimide contains one or more diphenyl sulfidegroups in its polyimide main chain.
 14. The composition according toclaim 13, wherein said diphenyl sulfide group is the diphenyl sulfidegroup in 4,4′-diaminodiphenyl sulfide.
 15. The composition according toany one of claims 1 to 3, wherein said polyimide contains one or morediphenyl disulfide groups in its polyimide main chain.
 16. Thecomposition according to claim 15, wherein said diphenyl disulphidegroup is the diphenyl disulphide group in 4,4′-diaminodiphenyldisulfide.
 17. The composition according to any one of claims 1 to 3,wherein said polyimide contains as one of aromatic diamine components,9,10-bis(4-aminophenyl)anthracene in its polyimide chain.
 18. Thecomposition according to any one of claims 1 to 3, wherein saidpolyimide contains an aromatic diamine having one or more biphenylsulfone groups in its polyimide chain.
 19. The composition according toclaim 18, wherein said aromatic diamine having one or more biphenylsulfone groups is at least one selected from the group consisting of3,3′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfone,bis-{4-(3-aminophenoxy)biphenyl}sulfone andbis-{4-(4-aminophenoxy)-biphenyl}sulfone.
 20. The composition accordingto claim 2 or 3, wherein said polyimide is composed of not less than 3components.
 21. The composition according to any one of claims 1 to 3,wherein said photoacid generator is a quinone diazide compound.
 22. Thecomposition according to any one of claims 1 to 3, which is in the formof a solution of said polyimide dissolved in a solvent, which solutioncontains said polyimide at a concentration of not less than 5% byweight.
 23. A positive-type photosensitive resin film prepared by makingsaid composition according to claim 22 in the form of film.
 24. Thepolyimide contained in said composition according to any one of claims 2to
 3. 25. The composition according to claim 1, wherein said polyimidecontains as an aromatic diamine component one aromatic diamine componentselected from the group consisting of 4,4′-diaminodiphenyl ether,3,4′-diaminodiphenyl ether, bis(4-phenoxy)1,4-benzene,bis(3-phenoxy)1,4-benzene, bis(3-phenoxy)1,3-benzene,2,2-bis(4-aminophenyl)propane,1,1,1,3,3,3-hexafluoro-2-bis(4-aminophenyl)propane,4,4′-diaminodiphenylmethane, bis(4-aminophenoxy)4,4′-diphenyl,2,2-bis{(4-aminophenoxy)phenyl}propane,2,2-bis{(4-aminophenoxy)phenyl}hexafluoropropane, 1,3-diaminobenzene,1,4-diaminobenzene, 2,4-diaminotoluene,3,3′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis(trifluoromethyl)benzidine,α,α′-bis(4-aminophenyl)-1,4-diisopropylbenzene,bis(4-aminophenoxy)-1,3-(2,2-dimethyl)propane and diaminosiloxane;wherein said polyimide has a weight average molecular weight in terms ofpolystyrene of 25,000 to 400,000, and has a thermaldecomposition-starting temperature of not lower than 450° C.
 26. Thecomposition according to claim 25, wherein said polyimide contains as anacid component at least one selected from the group consisting of3,4,3′,4′-benzophenone tetracarboxylic dianhydride,3,4,3′,4′-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride2,3,3′,4′-biphenyl ether tetracarboxylic dianhydride,1,2,5,6-naphthalene carboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,3′,4′-biphenyl sulfone tetracarboxylicdianhydride, bicyclo(2,2,2)-oct-7-ene-2,3,5,6-tetracarboxylicdianhydride and4,4′-{2,2,2-trifluoro-1-(trifluoromethyl)ethylidene}bis(1,2-benzenedicarboxylicdianhydride).
 27. The composition according to claim 25 or 26, whereinsaid weight average molecular weight is, 30,000 to 200,000.
 28. Thecomposition according to claim 25 or 26, wherein said photoacidgenerator is a quinone diazide compound.
 29. The composition accordingto claim 25 or 26, which is in the form of a solution of said polyimidedissolved in a solvent, which solution contains said polyimide at aconcentration of not less than 5% by weight.
 30. Positive-typephotosensitive polyimide compositions comprising a photoacid generatorand a solvent-soluble polyimide (excluding those having phenolichydroxyl group, carboxyl group, thiophenol group, or sulfonic acidgroup, or a derivative of any of said groups which yields any of saidgroups by action of said photoacid generator) which shows positivephotosensitivity in the presence of said photoacid generator, whereinsaid polyimide is formed by polycondensation between one or moretetracarboxylic dianhydrides and one or more aromatic diamines, whereinone of the aromatic diamine components is a nitro aromatic diamine. 31.The composition according to claim 30, wherein said nitro aromaticdiamine component is 1,4-diamino-2-nitrobenzene and/or3,3′-dinitro-4,4′-diaminobiphenyl.
 32. Positive-type photosensitivepolyimide compositions comprising a photoacid generator and asolvent-soluble polyimide (excluding those having phenolic hydroxylgroup, carboxyl group, thiophenol group, or sulfonic acid group, or aderivative of any of said groups which yields any of said groups byaction of said photoacid generator) which shows positivephotosensitivity in the presence of said photoacid generator, whereinsaid polyimide is formed by polycondensation between one or moretetracarboxylic dianhydrides and one or more aromatic diamines, whereinsaid polyimide contains 1,4-bis-(3-aminopropyl)piperazine together withan aromatic diamine in its polyimide main chain.
 33. Positive-typephotosensitive polyimide compositions comprising a photoacid generatorand a solvent-soluble polyimide (excluding those having phenolichydroxyl group, carboxyl group, thiophenol group, or sulfonic acidgroup, or a derivative of any of said groups which yields any of saidgroups by action of said photoacid generator) which shows positivephotosensitivity in the presence of said photoacid generator, whereinsaid polyimide is formed by polycondensation between one or moretetracarboxylic dianhydrides and one or more aromatic diamines, whereinsaid polyimide contains3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro-(5,5)-undecane togetherwith an aromatic diamine in its polyimide main chain.
 34. Positive-typephotosensitive polyimide compositions comprising a photoacid generatorand a solvent-soluble polyimide (excluding those having phenolichydroxyl group, carboxyl group, thiophenol group, or sulfonic acidgroup, or a derivative of any of said groups which yields any of saidgroups by action of said photoacid generator) which shows positivephotosensitivity in the presence of said photoacid generator, whereinsaid polyimide is formed by polycondensation between one or moretetracarboxylic dianhydrides and one or more aromatic diamines, and saidcomposition is obtained by heating and dehydrating an acid dianhydrideand an aromatic diamine at a molar ratio of 1.05 to 0.95 in a polarsolvent in the presence of an acid catalyst generated by reactionbetween a lactone and a base.
 35. The composition according to claim 34,wherein said lactone is γ-valerolactone and said base is pyridine and/ormethylmorpholine.
 36. The composition according to claim 34, whereinsaid polyimide is a block copolymer having a molar ratio of totalaromatic diamines to total tetracarboxylic anhydrides of 1.05 to 0.95,which is obtained by two-step polycondensation including preparing apolyimide oligomer by reaction between an aromatic diamine as a diaminecomponent and a tetracarboxylic anhydride as an acid component whereinone of said aromatic diamine or said tetracarboxylic anhydride is usedin excess, and when preparing said polyimide by adding said aromaticdiamine and/or said tetracarboxylic anhydride.
 37. The compositionaccording to claim 36, wherein said block copolymer polyimide is formedby polycondensation using lactone-base as a catalyst, which polyimide isin the form of a solution dissolved in a polar solvent at aconcentration of not less than 5% by weight, which polyimide has anaverage molecular weight of 25,000 to 400,000.
 38. Positive-typephotosensitive polyimide compositions comprising a photoacid generatorand a solvent-soluble polyimide (excluding those having phenolichydroxyl group, carboxyl group, thiophenol group, or sulfonic acidgroup, or a derivative of any of said groups which yields any of saidgroups by action of said photoacid generator) which shows positivephotosensitivity in the presence of said photoacid generator, whereinsaid polyimide is formed by polycondensation between one or moretetracarboxylic dianhydrides and one or more aromatic diamines, and saidpolyimide has a weight average molecular weight in terms of polystyreneof 25,000 to 400,000, and has a thermal decomposition-startingtemperature of not lower than 450° C.
 39. The composition according toclaim 38, wherein said weight average molecular weight is 30,000 to200,000.
 40. Positive-type photosensitive polyimide compositionscomprising a photoacid generator and a solvent-soluble polyimide(excluding those having phenolic hydroxyl group, carboxyl group,thiophenol group, Or sulfonic acid group, or a derivative of any of saidgroups which yields any of said groups by action of said photoacidgenerator) which shows positive photosensitivity in the presence of saidphotoacid generator, wherein said polyimide is formed bypolycondensation between one or more tetracarboxylic dianhydrides andone or more aromatic diamines, wherein one of the aromatic diaminecomponents is dialkyl-diamino-biphenyl sulfone, and wherein saidpositive-type photosensitive polyimide compositions contains saidphotoacid generator in an amount of 10 to 50% by weight based on theweight of said polyimide.
 41. A polyimide insulation film having apattern which is prepared by: coating said composition according toclaim 22 on a substrate, drying the composition, exposing an imagepattern on the composition to irradiation of light or electron beam, andremoving the exposed regions with an alkaline developing solution.
 42. Amethod for forming a polyimide insulation film pattern comprising:coating said composition according to claim 22 on a substrate, dryingthe composition, exposing an image pattern on the composition toirradiation of light or electron beam having a wavelength of 250 to 450nm, and removing the exposed regions with an alkaline developingsolution.
 43. The method according to claim 4, wherein said alkalinesolution is aminoalcohol.
 44. A positive-type photosensitive resin filmprepared by making said composition according to claim 37 in the form offilm.
 45. A polyimide insulation film having a pattern, which isprepared by: coating said composition according to claim 37 on asubstrate, drying the composition, exposing an image pattern on thecomposition to irradiation of light or electron beam, and removing theexposed regions with an alkaline developing solution.
 46. A method forforming a polyimide insulation film pattern comprising: coating saidcomposition according to claim 37 on a substrate, drying thecomposition, exposing an image pattern on the composition to irradiationof light or electron beam, and removing the exposed regions with analkaline developing solution.